U.S. patent application number 13/519172 was filed with the patent office on 2012-11-15 for coating composition and sheet using same.
This patent application is currently assigned to DAI NIPPON PRINTING CO., LTD.. Invention is credited to Takehiko Hiroshima, Akiko Inoue, Jun Kaneki, Takeshi Kobayashi, Hiroaki Takahashi, Yoko Takano.
Application Number | 20120288718 13/519172 |
Document ID | / |
Family ID | 44226603 |
Filed Date | 2012-11-15 |
United States Patent
Application |
20120288718 |
Kind Code |
A1 |
Takano; Yoko ; et
al. |
November 15, 2012 |
COATING COMPOSITION AND SHEET USING SAME
Abstract
Provided are a coating composition which provides a sheet with a
visible light transmission property and a UV ray-blocking
performance in addition to an excellent self-cleaning performance
and a persistence thereof, a weatherability and a persistence
thereof and a transparency and a sheet having a surface protective
layer formed by the above composition. They are a coating
composition comprising an ionizing radiation-curable resin and a
hydrophilizing agent such as a silicate compound and alkyl silicate
and a sheet having a surface protective layer formed by
cross-linking and curing the above coating composition.
Inventors: |
Takano; Yoko; (Tokyo,
JP) ; Kobayashi; Takeshi; (Tokyo, JP) ;
Hiroshima; Takehiko; (Tokyo, JP) ; Kaneki; Jun;
(Okayama, JP) ; Takahashi; Hiroaki; (Okayama,
JP) ; Inoue; Akiko; (Okayama, JP) |
Assignee: |
DAI NIPPON PRINTING CO.,
LTD.
Tokyo
JP
|
Family ID: |
44226603 |
Appl. No.: |
13/519172 |
Filed: |
December 28, 2010 |
PCT Filed: |
December 28, 2010 |
PCT NO: |
PCT/JP2010/073766 |
371 Date: |
June 26, 2012 |
Current U.S.
Class: |
428/423.1 ;
252/589 |
Current CPC
Class: |
Y10T 428/31551 20150401;
C08K 5/3475 20130101; C09D 175/16 20130101; C08G 18/672 20130101;
C08G 18/672 20130101; C08G 18/672 20130101; C08G 18/672 20130101;
C09D 7/48 20180101; C09D 5/1618 20130101; C08G 18/44 20130101; C09D
5/1637 20130101; C08G 18/42 20130101; C08G 18/62 20130101; C08K
5/3492 20130101 |
Class at
Publication: |
428/423.1 ;
252/589 |
International
Class: |
G02B 5/22 20060101
G02B005/22; B32B 27/06 20060101 B32B027/06 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 28, 2009 |
JP |
2009-298802 |
Mar 30, 2010 |
JP |
2010-079753 |
Mar 30, 2010 |
JP |
2010-079754 |
Jul 30, 2010 |
JP |
2010-173027 |
Claims
1. A coating composition comprising caprolactone base urethane
(meth)acrylate, a triazine base UV absorber and a hindered amine
base light stabilizer having a reactive functional group A1.
2. The coating composition according to claim 2, wherein the
reactive functional group A1 is a (meth)acryloyl group.
3. The coating composition according to claim 1, further comprising
a silicate compound having a reactive functional group B1 or alkyl
silicate.
4. The coating composition according to claim 3, wherein the
reactive functional group B1 is a (meth)acryloyl group.
5. A coating composition comprising an ionizing radiation-curable
resin and a silicate compound, wherein the above silicate compound
has a reactive functional group B2.
6. The coating composition according to claim 5, wherein the
reactive functional group B2 is a (meth)acryloyl group.
7. The coating composition according to claim 5, wherein the
ionizing radiation-curable resin is caprolactone base urethane
(meth)acrylate.
8. A coating composition comprising caprolactone base urethane
(meth)acrylate, a silicate compound having a reactive functional
group B3 or alkyl silicate and a triazine base UV absorber and/or a
benzotriazole base UV absorber.
9. The coating composition according to claim 8, wherein the
reactive functional group B3 is a (meth)acryloyl group.
10. A coating composition comprising an ionizing radiation-curable
resin and a silicate compound, wherein the above silicate compound
is alkyl silicate having a methoxy group.
11. The coating composition according to claim 10, wherein the
alkyl silicate has a molecular weight of 150 to 2500.
12. The coating composition according to claim 10, wherein the
ionizing radiation-curable resin is caprolactone base urethane
(meth)acrylate.
13. The coating composition according to claim 10, comprising a
triazine base UV absorber and/or a hindered amine base light
stabilizer.
14. A coating composition comprising an ionizing radiation-curable
resin and a silicate compound, wherein the above silicate compound
is alkyl silicate of an eicosamer to a 40-mer.
15. The coating composition according to claim 14, wherein the
alkyl silicate has a methoxy group.
16. The coating composition according to claim 14, wherein the
ionizing radiation-curable resin is caprolactone base urethane
(meth)acrylate.
17. The coating composition according to claim 14, comprising a
triazine base UV absorber and/or a hindered amine base light
stabilizer.
18. A sheet having a surface protective layer formed by
cross-linking and curing the coating composition according to claim
1.
19. The sheet according to claim 18, wherein it comprises at least
a base material and a surface protective layer, and the above
surface protective layer is provided on an outermost surface.
20. The sheet according to claim 19, wherein a primer layer is
provided between a film of the base material film and the surface
protective layer.
21. A sheet having a surface protective layer formed by
cross-linking and curing the coating composition according to claim
5.
22. A sheet having a surface protective layer formed by
cross-linking and curing the coating composition according to claim
8.
23. A sheet having a surface protective layer formed by
cross-linking and curing the coating composition according to claim
10.
24. A sheet having a surface protective layer formed by
cross-linking and curing the coating composition according to claim
14.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a coating composition and a
sheet prepared by using the same.
RELATED ART
[0002] Entrance doors and exterior materials in general housings,
interiors and exteriors such as floor materials, outside walls and
the like in public facilities, buildings and structures installed
outdoors are exposed daily to direct rays and wind and weather, and
therefore a very severe weatherability is required to sheets used
for protecting the surfaces of these interior and exterior
materials and structures. Various sheets are investigated in order
to enhance the weatherability (refer to patent documents 1 to
3).
[0003] In all of the patent documents 1 to 3, the weatherability is
attempted to be enhanced by adding additives such as a light
stabilizer, a UV absorber and the like to the protective layer.
However, when the addition amounts of the additives contained in
the above protective layer are elevated, these additives bleed out
due to a compatibility thereof with a binder resin forming the
protective layer to cause stickiness. On the other hand, if the
addition amounts stay in such an extent that they do not bleed out,
the satisfactory performances of the additives are not obtained,
and the problem that the sheets which are satisfactory in terms of
a weatherability are not obtained has been involved therein.
[0004] On the other hand, contaminants such as dusts, coarse
particulates, oily matters and the like are liable to be adhered on
the interior and exterior materials and the structures described
above, and when they are exposed to wind and weather in a state in
which the above contaminants are adhered thereon, the contaminants
remain in the form of lines along rain stripes, so that the problem
that the appearance thereof is notably reduced is involved therein.
Accordingly, an antifouling property is required as well to sheets
used for the surfaces of the interior and exterior materials and
the structures described above. Usually, used for enhancing the
antifouling property is a method in which a hydrophilicity of the
protective layer is enhanced by using an additive such as silica
and the like in addition to a method in which silicones and
fluorine compounds are blended. However, the problem that a large
amount of the additives has to be used in order to secure the
sufficiently high antifouling property and the problems that this
allows the additives to drop off from the protective layer and that
the hydrophilicity is reduced due to scratches have been involved
therein. Further, it is described in a patent document 4 that an
organosilicate compound is employed as an additive. Also in the
above case, however, the problems of requiring a large amount of
the additive, dropping off of the additive and a reduction in the
hydrophilicity due to scratches each described above have not come
to be solved.
[0005] Further, a weatherability, an antifouling property and a
self-cleaning capability of the sheets used for the interior and
exterior materials and the structures described above are paid
attentions, and they have come to be requested to be applied to
such uses that a transparency is required as is the case with, for
example, a protective sheet for window glasses, vinyl houses and
the like. It is generally known that when a light absorber and a UV
absorber are added to a protective layer, a reduction in the
transparency and decoloration such as yellowing are brought about,
and in production of sheets for application in which a transparency
is required, the sheets stay in a situation in which severer issue
is imposed.
[0006] Films comprising an olefin base film and vinyl chloride base
film as a base film are developed in large numbers as agricultural
films used for vinyl houses and the like (refer to, for example, a
patent document 5). In general, however, it is known that a
weatherability of olefin base films is not sufficiently high, and
the problem that they can not stand use over a long period of time
is present. Further, a method in which a coating film is formed on
an olefin base film by coating to provide it with functions such as
a weatherability and the like is employed as well, but films which
can meet at the same time, various performances described above
which are required to agricultural films have not been found
out.
[0007] Further, agricultural films comprising a fluorine base resin
film as a base material are known as films having an excellent
weatherability (refer to, for example, a patent document 6).
However, when a fluorine base resin film is used as a base
material, it is hard and therefore is not satisfactory in terms of
a workability, and since it has basically a quality of having a
mold releasing property, it is not satisfactory in terms of a film
formability by coating and a persistence thereof and has involved
the problem that it can not meet providing a functionality
according to vegetables. [0008] Patent document 1: Japanese Patent
Application Laid-Open No. 245442/2007 [0009] Patent document 2:
Japanese Patent Application Laid-Open No. 66966/2009 [0010] Patent
document 3: Japanese Patent Application Laid-Open No. 66967/2009
[0011] Patent document 4: Japanese Patent No. 2869443 [0012] Patent
document 5: Japanese Patent Application Laid-Open No. 180169/2003
[0013] Patent document 6: Japanese Patent Application Laid-Open No.
34249/1999
BRIEF EXPLANATION OF THE DRAWINGS
[0014] FIG. 1 is a schematic drawing showing a cross section of the
sheet in the present invention.
[0015] FIG. 2 is a schematic drawing showing another embodiment of
a cross section of the sheet in the present invention.
[0016] FIG. 3 is a schematic drawing showing a different embodiment
of a cross section of the sheet in the present invention.
[0017] FIG. 4 is a schematic drawing showing a cross section of the
coating film in the present invention.
EXPLANATION OF CODES
[0018] 1. Sheet [0019] 2. Base material [0020] 3. Pattern-printed
layer [0021] 3a. Picture layer [0022] 3b. Colored layer [0023] 4.
Transparent resin layer [0024] 5. Primer layer [0025] 6. Surface
protective layer [0026] 7. Rear face primer layer [0027] 8.
Adhesive layer [0028] 9. Colored resin layer
[0029] An object of the present invention is to solve the above
problems and provide a coating composition which provides a sheet
with a visible light transmission property and a UV ray-blocking
performance in addition to an excellent self-cleaning performance
and a persistence thereof, a weatherability and a persistence
thereof and a transparency and a sheet having a surface protective
layer formed by the above composition.
[0030] Intense researches repeated by the present inventors in
order to achieve the object described above have resulted in
finding that the problems described above can be solved by a
coating composition comprising a specific ionizing
radiation-curable resin or a specific silicate compound and having
the following constitution and a sheet prepared by using the same.
The present invention has been completed based on the above
knowledge.
[0031] That is, the essential points of the present invention are
shown below.
1. A coating composition comprising caprolactone base urethane
(meth)acrylate, a triazine base UV absorber and a hindered amine
base light stabilizer having a reactive functional group A1. 2. The
coating composition according to the item 1 described above,
further comprising a silicate compound having a reactive functional
group B1 or alkyl silicate. 3. A coating composition comprising an
ionizing radiation-curable resin and a silicate compound, wherein
the above silicate compound has a reactive functional group B2. 4.
The coating composition according to the item 3 described above,
wherein the ionizing radiation-curable resin is caprolactone base
urethane (meth)acrylate. 5. A coating composition comprising
caprolactone base urethane (meth)acrylate, a silicate compound
having a reactive functional group B3 or alkyl silicate and a
triazine base UV absorber and/or a benzotriazole base UV absorber.
6. A coating composition comprising an ionizing radiation-curable
resin and a silicate compound, wherein the above silicate compound
is alkyl silicate having a methoxy group. 7. The coating
composition according to the item 6 described above, wherein the
ionizing radiation-curable resin is caprolactone base urethane
(meth)acrylate. 7. The coating composition according to the item 6
or 7 described above, comprising a triazine base UV absorber and/or
a hindered amine base light stabilizer. 8. A coating composition
comprising an ionizing radiation-curable resin and a silicate
compound, wherein the above silicate compound is alkyl silicate of
an eicosamer to a 40-mer. 9. The coating composition according to
the item 8 described above, wherein the ionizing radiation-curable
resin is caprolactone base urethane (meth)acrylate. 10. The coating
composition according to the item 8 or 9 described above,
comprising a triazine base UV absorber and/or a hindered amine base
light stabilizer. 11. A sheet having a surface protective layer
prepared by cross-linking and curing the coating composition
according to any of the items 1 to 10. 12. The sheet according to
the item 11 described above, wherein it comprises at least a base
material and a surface protective layer, and the above surface
protective layer is provided on an outermost surface. 13. The sheet
according to the item 11 or 12 described above, wherein primer
layer is provided between the base material film and the surface
protective layer.
[0032] According to the present invention, capable of being
provided are a coating composition which provides a sheet with a
visible light transmission property and a UV ray-blocking
performance in addition to an excellent self-cleaning performance
and a persistence thereof, a weatherability and a persistence
thereof and a transparency and a sheet having a surface protective
layer which is formed by the above composition.
BEST MODE FOR CARRYING OUT THE INVENTION
Coating Composition 1:
[0033] A first embodiment of the coating composition in the present
invention (hereinafter referred to merely as the "coating
composition 1") is a coating composition comprising caprolactone
base urethane (meth)acrylate, a triazine base UV absorber and a
hindered amine base light stabilizer having a reactive functional
group A1. The respective components shall be explained below.
<<Caprolactone Base Urethane(Meth)Acrylate>>
[0034] The caprolactone base urethane (meth)acrylate used in the
present invention is a resin having an ionizing radiation-curing
property and can be obtained usually by reacting a caprolactone
base polyol and organic isocyanate with hydroxy(meth)acrylate. In
this connection, an ionizing radiation means a radiation having an
energy quantum which can polymerize or cross-link molecules among
electromagnetic waves and charged particle beam, and an ultraviolet
ray (UV) or an electron beam (EB) is usually used. In addition
thereto, electromagnetic waves such as an X ray, a .gamma. ray and
the like and charged particle beams such as an .alpha. ray, an ion
beam and the like can be used as well.
[0035] In this respect, commercially available polyols can be used
for the caprolactone base polyol, and they include polyols which
have preferably two hydroxyl groups and which have a weight average
molecular weight of preferably 500 to 3000, more preferably 750 to
2000. Further, polyols other than the caprolactone base, for
example, polyols such as ethylene glycol, diethylene glycol,
1,4-butanediol, 1,6-hexanediol and the like can be used as well
alone or in a mixture of plural kinds thereof in an optional
proportion.
[0036] The organic polyisocyanate is preferably diisocyanate having
two isocyanate groups, and it includes preferably
isophoronediisocyanate, hexamethylenediisocyanate,
4,4'-dicyclohexylmethanediisocyanate,
trimethylhexamethylene-diisocyanate and the like from the viewpoint
of inhibiting yellowing. Also, the hydroxy(meth)acrylate includes
preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
caprolactone-modified 2-hydroxyethyl acrylate and the like.
[0037] The caprolactone base urethane (meth)acrylate can be
synthesized by reacting these caprolactone base polyol and organic
isocyanate with the hydroxy(meth)acrylate. A synthetic method
thereof is preferably a method in which the caprolactone base
polyol is reacted with the organic isocyanate to form a
polyurethane prepolymer having --NCO groups (isocyanate groups) at
both ends and in which the polyurethane prepolymer is then reacted
with the hydroxy(meth)acrylate. The conditions of the reaction can
be based on those of an ordinary method.
[0038] The caprolactone base urethane (meth)acrylate used in the
present invention has a weight average molecular weight (weight
average molecular weight reduced to polystyrene which is measured
by a GPC method) of preferably 1000 to 10000, more preferably 2000
to 10000. That is, the caprolactone base urethane (meth)acrylate is
preferably an oligomer. If the weight average molecular weight
falls in the ranges (oligomer) described above, the processability
is excellent, and the coating composition is provided with a
suitable thixotropic property, so that the surface protective layer
is readily formed.
<<Triazine Base UV Absorber>>
[0039] The triazine base UV absorber used in the present invention
is preferably a hydroxyphenyltriazine base UV absorber. The above
UV absorber includes preferably, for example,
2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)--
1,3,5-triazine,
2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dim-
ethylphenyl)-1,3,5-triazine,
2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine,
2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-di-
methylphenyl)-1,3,5-triazine,
2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dime-
thylphenyl)-1,3,5-triazine and the like. They can be used alone or
in combination of plural kinds thereof.
[0040] A content of the triazine base UV absorber is preferably 1
to 10 parts by mass, more preferably 3 to 10 parts by mass and
further preferably 5 to 10 parts by mass based on 100 parts by mass
of the caprolactone base urethane (meth)acrylate. If a content of
the triazine base UV absorber falls in the ranges described above,
the above absorber does not bleed out, and the sufficiently high UV
absorbability is obtained, so that the excellent weatherability is
obtained. In general, if 1 part by mass or more of a UV absorber
based on 100 parts by mass of a binder resin is added, the above
absorber bleeds out in a certain case, and therefore the more
excellent UV absorbability has not so far been obtained if tried to
be obtained. According to the present invention, however,
combination of the triazine base UV absorber, the caprolactone base
urethane (meth)acrylate and the prescribed light stabilizer has
made it possible to obtain the excellent weatherability without
allowing the UV absorber to bleed out even if adding the UV
absorber in such a large amount as 1 part by mass or more.
<<Hindered Amine Base Light Stabilizer Having a Reactive
Functional Group A1>>
[0041] In the hindered amine base light stabilizer used in the
present invention, the reactive functional group A1 shall not
specifically be restricted as long as it has a reactivity with the
caprolactone base urethane (meth)acrylate and includes preferably,
for example, functional groups having an ethylenical double bond
such as a (meth)acryloyl group, a vinyl group, an allyl group and
the like, and it is preferably at least one selected from them.
Among them, the (meth)acryloyl group is preferred.
[0042] The above light stabilizer includes
1,2,2,6,6-pentamethyl-4-piperidyl methacrylate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate,
methyl(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate,
2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)ami-
no]-6-(2-hydroxyethylamine)-1,3,5-triazine) and the like.
[0043] A content of the hindered amine base light stabilizer having
a reactive functional group A1 is preferably 1 to 10 parts by mass,
more preferably 3 to 10 parts by mass and further preferably 5 to
10 parts by mass based on 100 parts by mass of the caprolactone
base urethane (meth)acrylate. If a content of the hindered amine
base light stabilizer falls in the ranges described above, the
above light stabilizer does not bleed out, and the sufficiently
high light stability is obtained, so that the excellent
weatherability is obtained.
<<Silicate Compound Having a Reactive Functional Group
B1>>
[0044] In the present invention, the silicate compound is used, if
desired, in order to provide a matter coated with the coating
composition of the present invention with a self-cleaning property.
The silicate compound used in the present invention shall not
specifically be restricted as long as it is a silicate compound
having a reactive functional group B1 having a reactivity with the
caprolactone base urethane (meth)acrylate. The reactive functional
group B1 includes preferably functional groups having an
ethylenical double bond such as a (meth)acryloyl group, a vinyl
group, an allyl group and the like, and it is preferably at least
one selected from them. Among them, the (meth)acryloyl group is
preferred.
[0045] The silicate compound having a reactive functional group B1
is Preferably a Compound Represented by the Following Formula
(1):
##STR00001##
[0046] In Formula (1), R.sup.1 to R.sup.3 represent a hydrogen atom
or an organic group having 1 to 10 carbon atoms, and plural R.sup.1
and R.sup.2 may be the same or different. Also, R.sup.4 is a
functional group containing a reactive functional group B1.
[0047] The organic group having 1 to 10 carbon atoms includes
preferably an alkyl group, an alkenyl group, a cycloalkyl group, an
aryl group, an aralkyl group and the like. The above groups may be
or may not be substituted, and the alkyl group and the alkenyl
group may be linear or branched. Among them, the alkyl group having
1 to 4 carbon atoms is more preferred.
[0048] Further, n.sub.1 is preferably 1 to 30, more preferably 1 to
10. That is, the silicate compound having a reactive functional
group .alpha. is preferably the silicate compound represented by
Formula (1) or a condensation product thereof, and the condensation
product is preferably a dimer to a 30-mer, more preferably a dimer
to a decamer. When the hydrophilizing agent is a condensation
product of the silicate compound, the preferred dimer to 30-mer or
the more preferred dimer to decamer described above includes a case
in which it is an average value.
[0049] To be more specific, the silicate compound is preferably a
compound represented by the following Formula (2):
##STR00002##
[0050] In Formula (2), R.sup.5 to R.sup.7 each are the same as
R.sup.1 to R.sup.3. R.sup.11 is the same as R.sup.1 and is
particularly preferably a hydrogen atom or methyl. Further, R.sup.9
and R.sup.10 represent a single bond or a divalent organic group.
Also, R.sup.9 represents a single bond, a carbonyl group (--CO--),
an ether bond (--O--), an ester bond (--COO--), a thioether bond
(--S--), an amide bond (--CONH--), an imino bond (--NH--), a
carbonate bond (--OCOO--) or a group obtained by connecting a
plurality of the above groups. The divalent organic group includes
preferably an alkanediyl group, an alkenediyl group, an arylene
group, an arylenealkanediyl group and the like. The above groups
may be or may not be substituted, and the alkanediyl group and the
alkenediyl group may be linear or branched. Among them, the
alkanediyl group having 1 to 4 carbon atoms is more preferred.
R.sup.9 is more preferably the ester bond (--COO--).
[0051] Further, n.sub.2 is the same as n.sub.1 described above.
[0052] A content of the silicate compound having a reactive
functional group B1 is preferably 1 to 15 parts by mass, more
preferably 3 to 15 parts by mass and further preferably 5 to 15
parts by mass based on 100 parts by mass of the caprolactone base
urethane (meth)acrylate. If a content of the silicate compound
falls in the ranges described above, a good cross-linking state of
the caprolactone base urethane (meth)acrylate is obtained. Further,
since the surface protective layer formed by using the coating
composition of the present invention comes to be provided with a
suited hydrophilicity, the wetting property to water is enhanced,
and the excellent self-cleaning property can be provided. That is,
interior and exterior materials and buildings are exposed to wind
and weather, but since the surface protective layer has a
hydrophilicity, a thin film is liable to be formed on the above
surface protective layer by rain water, and therefore contaminants
themselves are inhibited from being stuck or contaminants stuck are
liable to be removed.
<<Alkyl Silicate>>
[0053] In the present invention, the alkyl silicate is used, if
desired, in order to provide a matter coated with the coating
composition of the present invention with a self-cleaning property.
The alkyl silicate may be any one as long as it has at least one
alkoxyl group bonded to a Si atom, and it is preferably tetraalkyl
silicate represented by the following Formula (3):
##STR00003##
[0054] In Formula (3), R.sup.12 to R.sup.15 represent a hydrogen
atom or a linear or branched alkyl group having 1 to 10 carbon
atoms, and plural R.sup.12 and R.sup.15 may be the same or
different. Also, all of R.sup.12 to R.sup.15 are not hydrogen atoms
at the same time. R.sup.12 to R.sup.15 are preferably an alkyl
group having 1 to 4 carbon atoms, more preferably an alkyl group
having 1 and 2 carbon atoms from the viewpoint of enhancing the
self-cleaning performance and the visible light transmission
property.
[0055] The term n.sub.3 is preferably 1 to 40, more preferably 10
to 30 and further preferably 10 to 20 from the viewpoint of
enhancing the self-cleaning property. That is, the alkyl silicate
is preferably the alkyl silicate represented by Formula (3) or a
condensation product thereof, and the condensation product is
preferably a dimer to a 40-mer, more preferably a decamer to a
30-mer and further preferably a decamer to an eicosamer. In the
present invention, when the hydrophilizing agent is a condensation
product of the silicate compound, the preferred dimer to 40-mer,
the more preferred decamer to 30-mer or the further preferred
decamer to eicosamer described above includes a case in which it is
an average value. Accordingly, the condensation products comprising
40 or less-mers on average are included in the condensation
products of the alkyl silicate of a dimer to a 40-mer which are
preferably used in the present invention though the condensation
products larger than a 40-mer are contained therein as is the case
with, for example, alkyl silicate which is a mixture of a
pentadecamer to a 45-mer and which is an eicosamer on average.
[0056] A weight average molecular weight thereof is preferably 150
to 4000, more preferably 1000 to 3000 and further preferably 1000
to 2000.
<<Various Additives>>
[0057] The coating composition of the present invention can contain
various additives as long as the performances thereof are not
inhibited. The various additives include, for example, a
polymerization inhibitor, a cross-linking agent, an antistatic
agent, an adhesion improving agent, an antioxidant, a leveling
agent, a thixotropy-providing agent, a coupling agent, a
plasticizer, a defoaming agent, a filler, a solvent and the
like.
Coating Composition 2:
[0058] A second embodiment of the coating composition in the
present invention (hereinafter referred to merely as the "coating
composition 2") is a coating composition comprising an ionizing
radiation-curable resin and a silicate compound, wherein the above
silicate compound has a reactive functional group B2. The
respective components shall be explained below.
<<Ionizing Radiation-Curable Resin>>
[0059] Those suitably selected from polymerizable monomers and
polymerizable oligomers or prepolymers which have so far
conventionally been used as ionizing radiation-curable resins can
be used for the ionizing radiation-curable resin used in the second
embodiment of the coating composition in the present invention. The
resins which are less liable to bleed out and have a coating
property in a proportion of 95 to 100% in terms of a solid matter
content and which do not bring about curing shrinkage in curing are
preferred from the viewpoint of obtaining the good curing
characteristics. The representative examples of the above ionizing
radiation-curable resin shall be described below. "(Meth)acrylate"
means "acrylate" or "methacrylate".
[0060] The polymerizable monomer is suitably (meth)acrylate
monomers having a radically polymerizable unsaturated group in a
molecule, and among them, multifunctional (meth)acrylates having
two or more ethylenically unsaturated bonds in a molecule are
preferred. They may be used alone or in combination of two or more
kinds thereof. The number of the functional groups is preferably 2
to 8, more preferably 2 to 6 and further preferably 3 to 4.
[0061] In the second embodiment of the coating composition in the
present invention, monofunctional (meth)acrylates such as
methyl(meth)acrylate and the like can suitably be used in
combination with the multifunctional (meth)acrylate described above
for the purpose of controlling a viscosity thereof as long as the
object of the present is not damaged. The monofunctional
(meth)acrylates may be used alone or in combination of two or more
kinds thereof.
[0062] Next, the polymerizable oligomer includes preferably
oligomers having radically polymerizable unsaturated group in a
molecule, for example, oligomers of an epoxy(meth)acrylate base, a
urethane (meth)acrylate base, polyether base urethane
(meth)acrylate, caprolactone base urethane (meth)acrylate, a
polyester(meth)acrylate base and a polyether(meth)acrylate base,
and the oligomers of a urethane (meth)acrylate base are more
preferred. Among the above oligomers, the multifunctional
polymerizable oligomers are preferred, and the number of the
functional groups is preferably 2 to 16, more preferably 2 to 8 and
further preferably 2 to 6.
[0063] Further, the polymerizable oligomer includes, in addition to
the above oligomers, highly hydrophobic polybutadiene(meth)acrylate
base oligomers having a (meth)acrylate group in a side chain of a
polybutadiene oligomer, silicone (meth)acrylate base oligomers
having a polysiloxane bond in a principal chain, aminoplast resin
(meth)acrylate base oligomers obtained by modifying an aminoplast
resin having many reactive groups in a small molecule and oligomers
having a cationic polymerizable functional group in a molecule such
as novolak type epoxy resins, bisphenol A type epoxy resins,
aliphatic vinyl ethers, aromatic vinyl ethers and the like. The
above polymerizable oligomers may be used alone or in combination
of two or more kinds thereof.
[0064] When a UV ray-curable resin is used as the ionizing
radiation-curable resin, an initiator for photopolymerization is
added preferably in a an amount of 0.1 to 5 parts by mass based on
100 parts by mass of the UV ray-curable resin. The initiator for
photopolymerization can suitably be selected from initiators which
have so far conventionally been used and shall not specifically be
restricted.
<Caprolactone Base Urethane(Meth)Acrylate>
[0065] Among the polymerizable oligomers described above, the
caprolactone base urethane (meth)acrylate is particularly preferred
since the weatherability and a persistence thereof and the
transparency in addition to the excellent self-cleaning property
are obtained by combination with the silicate compound having a
reactive functional group B2 described later. The caprolactone base
urethane (meth)acrylate is the same as explained in the first
embodiment of the coating composition.
<<Silicate Compound Having a Reactive Functional Group
B2>>
[0066] In the second embodiment of the coating composition in the
present invention, the silicate compound is used in order to
provide a matter coated with the coating composition of the present
invention with a self-cleaning property. The silicate compound used
in the present invention shall not specifically be restricted as
long as it is a silicate compound having a reactive functional
group B2 which has a reactivity with the caprolactone base urethane
(meth)acrylate. The silicate compound having a reactive functional
group B2 is the same as the silicate compound having a reactive
functional group B1 explained in the first embodiment of the
coating composition.
<<Alkyl Silicate Compound>>
[0067] In the second embodiment of the coating composition in the
present invention, the coating composition contains preferably the
alkyl silicate compound. The alkyl silicate compound is the same as
the alkyl silicate compound explained in the first embodiment of
the coating composition, and in the second embodiment of the
coating composition of the present invention, n.sub.3 in Formula
(3) is preferably 1 to 30, more preferably 5 to 15 from the
viewpoint of enhancing the self-cleaning performance and a
persistence thereof.
<<Hindered Amine Base Light Stabilizer>>
[0068] In the second embodiment of the coating composition in the
present invention, the coating composition contains preferably a
hindered amine base light stabilizer. The hindered amine base light
stabilizer shall not be restricted as long as it is a hindered
amine base light stabilizer, and it is preferably a hindered amine
base light stabilizer having a reactive functional group A2. The
hindered amine base light stabilizer having a reactive functional
group A2 is the same as the hindered amine base light stabilizer
having a reactive functional group A1 explained in the first
embodiment of the coating composition.
<<Triazine Base UV Absorber>>
[0069] In the second embodiment of the coating composition in the
present invention, the coating composition contains preferably a
triazine base UV absorber. The triazine base UV absorber is the
same as the triazine base UV absorber explained in the first
embodiment of the coating composition.
<<Various Additives>>
[0070] In the second embodiment of the coating composition in the
present invention, the coating composition can contain various
additives as long as the performances thereof are not inhibited.
The various additives include, for example, a polymerization
inhibitor, a cross-linking agent, an antistatic agent, an adhesion
improving agent, an antioxidant, a leveling agent, a
thixotropy-providing agent, a coupling agent, a plasticizer, a
defoaming agent, a filler, a solvent and the like.
Coating Composition 3:
[0071] A third embodiment of the coating composition in the present
invention (hereinafter referred to merely as the "coating
composition 3") is a coating composition comprising caprolactone
base urethane (meth)acrylate, a silicate compound having a reactive
functional group B3 or alkyl silicate and a triazine base UV
absorber and/or a benzotriazole base UV absorber. The respective
components shall be explained below.
<<Caprolactone Base Urethane (meth)acrylate>>
[0072] In the third embodiment of the coating composition in the
present invention, the coating composition contains the
caprolactone base urethane (meth)acrylate. This allows the
weatherability and the visible light transmission property in
addition to the excellent self-cleaning performance to be obtained.
The caprolactone base urethane (meth)acrylate is the same as
explained in the first embodiment of the coating composition.
<<Other Ionizing Radiation-Curable Resins>>
[0073] In the third embodiment of the coating composition in the
present invention, those suitably selected from polymerizable
monomers and polymerizable oligomers or prepolymers which have so
far conventionally been used as ionizing radiation-curable resins
can be used as the ionizing radiation-curable resin as long as the
effects thereof are not inhibited. The above ionizing
radiation-curable resins include preferably the ionizing
radiation-curable resins explained in the third embodiment of the
coating composition.
<<Silicate Compound Having a Reactive Functional Group B3 or
Alkyl Silicate>>
[0074] In the third embodiment of the coating composition in the
present invention, the coating composition contains the silicate
compound having a reactive functional group B3 or the alkyl
silicate as the hydrophilizing agent. Addition of the
hydrophilizing agent makes it possible to obtain the excellent
self-cleaning performance and the excellent visible light
transmission property. The silicate compound having a reactive
functional group B3 and the alkyl silicate each are the same as the
silicate compound having a reactive functional group B1 and the
alkyl silicate which have been explained in the first embodiment of
the coating composition.
<<UV Absorber>>
[0075] In the third embodiment of the coating composition in the
present invention, the coating composition contains the triazine
base UV absorber and/or the benzotriazole base UV absorber as the
UV absorber for the purpose of enhancing the weatherability, the UV
ray-blocking performance and the weatherability-keeping property.
In the third embodiment of the coating composition in the present
invention, the triazine base UV absorber and the benzotriazole base
UV absorber each can be used independently, and the triazine base
UV absorber and the benzotriazole base UV absorber are used
preferably in combination from the viewpoint of obtaining the
excellent weatherability, the excellent UV ray-blocking performance
and the excellent weatherability-keeping property. A blend mass
ratio thereof is preferably 10:90 to 90:10, more preferably 30:70
to 70:30. If the triazine base UV absorber and the benzotriazole
base UV absorber are used in combination, obtained are very
excellent effects in terms of inhibiting activities of harmful
insects and the weatherability-keeping property that the tensile
strength is good even after stretched for a long time in the
agricultural application as well as the weatherability.
[0076] In the third embodiment of the coating composition in the
present invention, the UV absorbing performance can flexibly be met
according to a large variety of applications. Among the triazine
base UV absorbers and the benzotriazole base UV absorbers, use of,
for example, the UV absorbers having a maximum absorption
wavelength in a range of 250 to 400 nm makes it possible to hold
off worms such as insects, harmful insects, moths and the like
which have a flying property of progressing toward a light source
having a wavelength in a UV region of the above range and makes it
possible to inhibit activities of the above harmful insects by
cutting off a prescribed UV region. Further, eggplants are
indispensably irradiated with a UV ray having a wavelength of 300
to 380 nm for growth thereof, and selecting a UV absorber which
absorbs the other UV rays while avoiding absorption of a UV ray of
the above range makes it possible to prepare an agricultural film
which is most suited to the application of growing eggplants.
<Triazine Base UV Absorber>
[0077] The triazine base UV absorber is the same as explained in
the first embodiment of the coating composition.
<Benzotriazole Base UV Absorber>
[0078] The benzotriazole base UV absorber includes
2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)-
phenyl]propionate, 2-2H-benzotriazole-2-yl)-6-(linear and side
chain dodecyl)-4-methylphenol,
2-[5-chloro(2H)-benzotriazole-2-yl]-4-methyl-6-(tert-butyl)phenol,
2-(2H-benzotriazole-2-yl)-4,6-di-tert-pentylphenol,
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole,
2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole,
2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole,
2-(2'-hydroxy-3'-(3'',4'',5'',6''-tetrahydrophthalimidemethyl)-5'-methylp-
henyl)benzotriazole,
2-2-methylenebis(4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazole-2-yl)ph-
enol,
2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole
and the like. They can be used alone or in combination of plural
kinds thereof.
[0079] A content of the UV absorber contained in the coating
composition is preferably 1 to 25 parts by mass, more preferably 2
to 15 parts by mass and further preferably 3 to 10 parts by mass
based on 100 parts by mass of the ionizing radiation-curable resin
(total of caprolactone base urethane (meth)acrylate and the other
ionizing radiation-curable resins which are used if desired). If a
content of the UV absorber falls in the ranges described above, the
above absorber does not bleed out, and the sufficiently high UV
absorbability is obtained, so that the excellent weatherability is
obtained.
<<Hindered Amine Base Light Stabilizer>>
[0080] In the third embodiment of the coating composition in the
present invention, the coating composition further contains
preferably a hindered amine base light stabilizer. It shall not be
restricted as long as it is a hindered amine base light stabilizer,
and it is preferably a hindered amine base light stabilizer having
a reactive functional group A2. The hindered amine base light
stabilizer having a reactive functional group A2 is the same as the
hindered amine base light stabilizer having a reactive functional
group A1 explained in the first embodiment of the coating
composition.
<<Various Additives>>
[0081] In the third embodiment of the coating composition in the
present invention, the coating composition can contain various
additives as long as the performances thereof are not inhibited.
The various additives include, for example, a polymerization
inhibitor, a cross-linking agent, an antistatic agent, an adhesion
improving agent, an antioxidant, a leveling agent, a
thixotropy-providing agent, a coupling agent, a plasticizer, a
defoaming agent, a filler, a solvent and the like.
Coating Composition 4:
[0082] A fourth embodiment of the coating composition in the
present invention (hereinafter referred to merely as the "coating
composition 4") is a coating composition comprising an ionizing
radiation-curable resin and a silicate compound, wherein the above
silicate compound is alkyl silicate having a methoxy group. The
respective components shall be explained below.
<<Ionizing Radiation-Curable Resin>>
[0083] The ionizing radiation-curable resin shall not specifically
be restricted, and capable of being used are transparent resins
comprising a prepolymer (including an oligomer) and/or a monomer as
a principal component which contain in a molecule, a radically
polymerizable double bond capable of being subjected to
polymerization cross-linking reaction by irradiating with an
ionizing radiation such as a UV ray, an electron beam and the like.
The above prepolymer and/or monomer can be used alone or in a
mixture of a plurality thereof. The curing reaction is usually
cross-linking curing reaction.
[0084] To be specific, the prepolymer or the monomer described
above includes compounds having in a molecule, a radically
polymerizable unsaturated group such as a (meth)acryloyl group, a
(meth)acryloyloxy group and the like, a cationic polymerizable
functional group such as an epoxy group and the like. Further,
prepolymers of a polyene/thiol base obtained by combining polyenes
with polythiols are preferred as well.
[0085] The prepolymer having a radically polymerizable unsaturated
group includes, for example, polyester (meth)acrylate, urethane
(meth)acrylate, epoxy(meth)acrylate, melamine(meth)acrylate,
triazine (meth)acrylate, silicone (meth)acrylate and the like. In
the present invention, particularly caprolactone base urethane
(meth)acrylate is preferably used as the ionizing radiation-curable
resin. When the caprolactone base urethane (meth)acrylate is used,
a weatherability of the coating composition is more enhanced. A
weight average molecular weight of the above prepolymers is
preferably 1000 to 10000, particularly preferably 1000 to 5000.
[0086] The monomer having a radically polymerizable unsaturated
group includes preferably, for example, monofunctional monomers
such as methyl(meth)acrylate, 2-ethylhexyl(meth)acrylate,
phenoxyethyl(meth)acrylate and the like. It include preferably, for
example, multifunctional monomers such as diethylene glycol
di(meth)acrylate, propylene glycol di(meth)acrylate,
trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene
oxide (meth)acrylate, dipentaerythritol tetra(meth)acrylate,
dipentaerythritol penta(meth)acrylate, dipentaerythritol
hexa(meth)acrylate and the like.
[0087] The prepolymer having a cationic polymerizable unsaturated
group includes, for example, prepolymers of epoxy base resins such
as bisphenol A type epoxy resins, novolak type epoxy resins and the
like and vinyl ether base resins such as fatty acid base vinyl
ethers, aromatic base vinyl ethers and the like. Also, the thiol
includes, for example, polythiols such as trimethylolpropane
trithioglycolate, pentaerythritol tetrathioglycolate and the like.
The polyene includes, for example, polyenes obtained by adding
allyl alcohol to both ends of polyurethane by diol and
isocyanate.
<<Alkyl Silicate>>
[0088] The alkyl silicate shall not specifically be restricted as
long as it has a methoxy group. To be specific, it is the same as
the alkyl silicate explained in the first embodiment of the coating
composition. In this regard, in the fourth embodiment of the
coating composition, at least any one of R.sup.12 to R.sup.15 in
formula (3) described above has to be methyl. That is, the alkyl
silicate used in the fourth embodiment of the coating composition
has to have a methoxy group.
[0089] In the fourth embodiment of the coating composition, the
above alkyl silicates are preferably monomers to eicosamers, more
preferably dimers to decamers. Also, a molecular weight thereof is
preferably 150 to 2500, more preferably 250 to 1500.
[0090] A content of the alkyl silicate contained in the coating
composition shall not be restricted, and the alkyl silicate
described above is contained in an amount of preferably 1 to 20
parts by mass, more preferably 6 to 10 parts by mass based on 100
parts by mass of the ionizing radiation-curable resin. If a content
of the alkyl silicate contained falls in the ranges described
above, a better cross-linking of the ionizing radiation-curable
resin is obtained, and the original performances (the scratch
resistance, the solvent resistance and the like) of the resin are
enhanced.
<<Additives>>
[0091] In the fourth embodiment of the coating composition, the
coating composition can be blended, if necessary, with publicly
known additives. The additives include a weather resistant agent
such as a UV absorber, a light stabilizer and the like and a
matting agent (gloss controlling agent). The UV absorber includes,
for example, benzophenone base UV absorbers, benzotriazole base UV
absorbers, triazine base UV absorbers and the like. The light
stabilizer is, for example, suitably a hindered amine base light
stabilizer. A content of the above weather resistant agents shall
not be restricted, and the contents of both the UV absorber and the
light stabilizer are preferably 1000 to 100000 ppm by weight.
Particularly in the fourth embodiment of the coating composition,
the triazine base UV absorber and/or the hindered amine base light
stabilizer are preferably used.
[0092] The matting agent includes publicly known inorganic
particles of silica and the like and organic pigments.
[0093] The coating composition of the present invention can be
prepared by mixing the components described above. They are mixed
by means of, for example, a publicly known kneading equipment such
as a Banbury mixer, a kneader blender, Brabende Plastograph, a
small-sized batch mixer, a continuous mixer, a mixing roll and the
like.
Coating Composition 5:
[0094] A fifth embodiment of the coating composition in the present
invention (hereinafter referred to merely as the "coating
composition 5") is a coating composition which comprising an
ionizing radiation-curable resin and a silicate compound, wherein
the above silicate compound is alkyl silicate of an eicosamer to a
40-mer. The respective components shall be explained below.
<<Alkyl Silicate>>
[0095] The alkyl silicate used in the fifth embodiment of the
coating composition in the present invention may be any one as long
as it has at least one alkoxy group bonded to a Si atom and has to
be a condensation product of an eicosamer to a 40-mer, and it is
preferably a condensation product of the tetraalkyl silicate
represented by Formula (3) described above. Also, in the fifth
embodiment of the coating composition of the present invention, at
least any one of R.sup.12 to R.sup.15 is preferably methyl. That
is, the alkyl silicate used in the fifth embodiment of the coating
composition of the present invention has preferably an alkoxyl
group having 1 to 4 carbon atoms, more preferably methoxy and
ethoxy and further preferably methoxy, and it has preferably at
least one methoxy.
[0096] The alkyl silicate used in the fifth embodiment of the
coating composition in the present invention is a condensation
product of an eicosamer to a 40-mer, and therefore n3 in Formula
(3) described above has to be 20 to 40. It is preferably 20 to 35,
more preferably 20 to 30 from the viewpoint of obtaining the
excellent self-cleaning property and the excellent transparency.
That is, the alkyl silicate used in the present invention has to be
a condensation product of an eicosamer to a 40-mer, and it is a
condensation product of preferably an eicosamer to a 35-mer, more
preferably an eicosamer to a 30-mer. In the fifth embodiment of the
coating composition in the present invention, the eicosamer to the
40-mer, the eicosamer to the 35-mer or the eicosamer to the 30-mer
includes a case in which it is an average value. Accordingly, the
alkyl silicate of an eicosamer or higher polymer on average though
the alkyl silicates of less than an eicosamer are contained therein
as is the case with, for example, alkyl silicate which is a mixture
of a pentadecamer to a 30-mer and which is a 25-mer on average is
included in the alkyl silicate used in the fifth embodiment of the
coating composition in the present invention.
[0097] A molecular weight of the alkyl silicate used in the fifth
embodiment of the coating composition in the present invention is
preferably 2500 to 4000, more preferably 2500 to 3500 and further
preferably 2500 to 3000. In the present invention, the molecular
weight includes a case in which it is an average value as is the
case with the polymers described above.
[0098] A content of the alkyl silicate is preferably 1 to 20 parts
by mass, more preferably 3 to 15 parts by mass and further
preferably 6 to 10 parts by mass based on 100 parts by mass of the
ionizing radiation-curable resin from the viewpoints that the
excellent self-cleaning property and the excellent transparency can
be obtained and that a state of better cross-linking curing in the
ionizing radiation-curable resin can be obtained.
<<Ionizing Radiation-Curable Resin>>
[0099] Those suitably selected from polymerizable monomers and
polymerizable oligomers or prepolymers which have so far
conventionally been used as ionizing radiation-curable resins can
be used for the ionizing radiation-curable resin used in the fifth
embodiment of the coating composition in the present invention. The
resins which are less liable to bleed out and have a coating
property in an extent of 95 to 100% in terms of a solid matter
content and which are less liable to bring about curing shrinkage
in curing are preferred from the viewpoint of obtaining the good
curing characteristics.
[0100] The above ionizing radiation-curable resin is the same as
explained in the second embodiment of the coating composition in
the present invention.
<Caprolactone Base Urethane (Meth)Acrylate>
[0101] Among the polymerizable oligomers described above, the
caprolactone base urethane (meth)acrylate is particularly preferred
since the weatherability and a persistence thereof and the
transparency in addition to the excellent self-cleaning property
are obtained by combining with alkyl silicate. The caprolactone
base urethane (meth)acrylate is the same as explained in the first
embodiment of the coating composition.
<<UV Absorber>>
[0102] In the fifth embodiment of the coating composition in the
present invention, the coating composition contains a UV absorber
for the purpose of enhancing the weatherability, the UV
ray-blocking performance and the weatherability-keeping property.
The UV absorber includes preferably a triazine base UV absorber, a
benzotriazole base UV absorber and the like. In this connection,
the triazine base UV absorber and the benzotriazole base UV
absorber are the same as those explained respectively in the first
embodiment and the third embodiment of the coating composition in
the present invention. The triazine base UV absorber and the
benzotriazole base UV absorber are used preferably in combination
from the viewpoint of obtaining the excellent weatherability, the
excellent UV ray-blocking performance and the excellent
weatherability-keeping property, and a blend mass ratio thereof is
preferably 10:90 to 90:10, more preferably 30:70 to 70:30.
[0103] In the fifth embodiment of the coating composition in the
present invention, a content of the UV absorber contained in the
coating composition is preferably 1 to 25 parts by mass, more
preferably 2 to 15 parts by mass and further preferably 3 to 10
parts by mass based on 100 parts by mass of the ionizing
radiation-curable resin. If a content of the UV absorber falls in
the ranges described above, the above absorber does not bleed out,
and the sufficiently high UV absorbing ability is obtained, so that
the excellent weatherability and the excellent transparency are
obtained.
<<Light Stabilizer>>
[0104] In the fifth embodiment of the coating composition in the
present invention, the coating composition further contains a light
stabilizer. The light stabilizer is preferably a hindered amine
base light stabilizer, more preferably a hindered amine base light
stabilizer having a reactive functional group A4. The hindered
amine base light stabilizer having a reactive functional group A4
is the same as the hindered amine base light stabilizer having a
reactive functional group A1 explained in the first embodiment of
the coating composition.
<<Various Additives>>
[0105] In the fifth embodiment of the coating composition in the
present invention, the coating composition can contain various
additives as long as the performances thereof are not inhibited.
The various additives include, for example, a polymerization
inhibitor, a cross-linking agent, an antistatic agent, an adhesion
improving agent, an antioxidant, a leveling agent, a
thixotropy-providing agent, a coupling agent, a plasticizer, a
defoaming agent, a filler, a solvent and the like.
Sheet 1:
[0106] A first embodiment of the sheet in the present invention
(hereinafter referred to merely as the "sheet 1") has a surface
protective layer which is obtained by cross-linking and curing the
coating composition 1, and it shall not specifically be restricted
as long as it has a surface protective layer. The sheet 1 of the
present invention can be formed from the above surface protective
layer alone, and preferred is an embodiment in which the surface
protective layer obtained by cross-linking and curing the coating
composition 1 is formed on a base material. The preferred
application of the sheet 1 of the present invention includes
applications requiring a transparency, an application to decorated
sheets and the like, and the sheet of the present invention shall
be explained below by application.
<<Applications Requiring a Transparency>>
[0107] First, a case in which the sheet 1 of the present invention
is used for applications requiring a transparency such as a
protective sheet for window glasses, vinyl houses and the like
shall be explained.
<Base Material>
[0108] In the sheet (hereinafter referred to as the sheet 1.alpha.)
of the present invention used for applications requiring a
transparency, the base material used therefor is preferably a
plastic film and a plastic sheet, and it includes preferably those
comprising a polyolefin resin, a vinyl base resin, a polyester
resin, an acryl resin, a polyamide resin, a cellulose base resin, a
polystyrene resin, a polycarbonate resin, a polyallylate resin, a
polyimide resin and the like.
[0109] The above base materials can be subjected, if desired, on
one face or both faces to physical and chemical surface treatments
including an oxidation method such as corona discharge treatment,
chrome oxidation treatment, hot blast treatment, ozone.cndot.UV ray
treatment and the like and a roughening method such as a sand blast
method, a solvent treating method and the like in order to enhance
an adhesive property with a layer provided thereon.
[0110] The above base materials may be subjected to treatments such
as forming a primer layer and a rear face primer layer for
reinforcing an interlayer adhesive property between the base
material and the surface protective layer and an adhesive property
with various adherends. A material used for forming the primer
layer shall not specifically be restricted and includes acryl base
resins, vinyl chloride/vinyl acetate copolymers, polyesters,
polyurethanes, chlorinated polypropylene and the like. A material
used for the rear face primer layer 7 is suitably selected
according to the adherends.
[0111] Further, painting for adjusting the color and patterns in
the viewpoint of the design may be formed in advance as long as the
transparency is not inhibited.
[0112] A thickness of the base materials shall not specifically be
restricted, and securing the durability and considering the general
versatility, it falls in a range of usually 20 to 200 .mu.m,
preferably 30 to 150 .mu.m.
<Surface Protective Layer>
[0113] The surface protective layer is a layer obtained by
cross-linking and curing the coating composition 1 of the present
invention. To be more specific, it is a layer formed by coating the
coating composition 1 on the base material described above and
cross-linking and curing it by irradiating with an ionizing
radiation.
[0114] The coating composition 1 is coated by a publicly known
method such as gravure coating, bar coating, roll coating, reverse
roll coating, comma coating and the like, preferably gravure
coating so that a thickness thereof after curing is set usually to
1 to 20 .mu.m. Also, it is preferably 2 to 20 .mu.m from the
viewpoint of obtaining the excellent weatherability and a
persistency thereof, the transparency and the antifouling
property.
[0115] An uncured resin layer formed by coating the coating
composition 1 of the present invention is cross-linked and cured by
irradiating with an ionizing radiation such as an electron beam, a
UV ray and the like, whereby it is turned into the surface
protective layer. In this regard, when an electron beam is used as
the ionizing radiation, an accelerating voltage thereof can
suitably be selected according to the resin used and a thickness of
the layer, and usually the uncured resin layer is cured preferably
at an accelerating voltage of 70 to 300 kV.
[0116] An irradiation dose is preferably a dose in which a
cross-linking density of the caprolactone base urethane
(meth)acrylate is saturated, and it is selected in a range of
usually 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1
to 5 Mrad).
[0117] The electron beam source shall not specifically be
restricted, and capable of being used are various electron beam
accelerating devices of, for example, a Cockroft-Walton type, a van
de Graaf type, a resonance transformer type, an insulating core
transformer type, a linear type, a Dynamitron type, a high
frequency type and the like.
[0118] Also, when a UV ray is used as the ionizing radiation, a ray
containing a UV ray having a wavelength of 190 to 380 nm is
radiated. The UV ray source shall not specifically be restricted,
and a high pressure mercury lamp, a low pressure mercury lamp, a
metal halide lamp, a carbon arc lamp and the like.
[0119] Also, the surface protective layer may have concave parts. A
method for providing concave parts on the surface protective layer
shall not specifically be restricted, and they are provided by, for
example, emboss processing. The emboss processing can be carried
out by a usual method using a publicly known embossing equipment of
a single layer type or a rotary type.
[0120] The sheet 1.alpha. thus obtained is provided with an
excellent weatherability and a persistency thereof and a
transparency, and it is provided with a more excellent antifouling
property when the silicate compound described above is contained in
the coating composition. It is suitably used for applications
requiring a transparency such as a protective sheet for window
glasses, PVC greenhouses and the like.
<<Decorated Sheet>>
[0121] The sheet 1 of the present invention is also suitably used
as a decorated sheet. For example, the sheet 1.alpha. used for the
applications requiring a transparency described above and the sheet
1.alpha. obtained by providing it with pictures can also be used as
the decorated sheet. A more preferred embodiment of the decorated
sheet shall be explained with reference to FIG. 1 to FIG. 3.
[0122] FIG. 1 and FIG. 2 are schematic drawings showing the cross
sections of the preferred embodiments of the sheet (hereinafter
referred to as the sheet 1.beta.) of the present invention which is
used as the decorated sheet. In the embodiment shown in FIG. 1, a
pattern-printed layer 3 and a surface protective layer 6 are
laminated in order on a base material 2, and in the embodiment
shown in FIG. 2, a pattern-printed layer 3, a transparent resin
layer 4, a primer layer 5 and a surface protective layer 6 formed
by cross-linking and curing the coating composition 1 of the
present invention are laminated in this order on a base material 2.
Also, in FIG. 2, a rear face primer layer 7 is provided on a rear
surface of the base material 2, and an adhesive layer 8 is provided
between the pattern-printed layer 3 and the transparent resin layer
4. Further, the transparent resin layer 4 has concave parts on a
surface at a primer layer side, and a colored resin layer 9
subjected to wiping against the above concave parts is provided.
The respective layers shall be explained below in detail.
<<Base Material 2>>
[0123] The base material 2 used in the sheet 1.beta. of the present
invention shall not specifically be restricted as long as it is
used usually for a decorated sheet, and various papers, woven
fabrics and non-woven fabrics of various fibers, plastic films,
plastic sheets, metal foils, metal sheets, wooden boards of lumbers
and the like, ceramic materials and the like can suitably be
selected according to the applications. The above materials each
may be used alone or in the form of laminated materials of optional
combinations such as composite materials of papers and composite
materials of papers and plastic films. Among them, the plastic
films and the plastic sheets are preferred considering a
processability, and above all, preferred are base materials of
polyolefin base resins such as polyethylene, polypropylene,
polybutene, polymethylpentene, ethylene/propylene copolymers,
ethylene/propylene/butene copolymers, polyolefin base thermoplastic
elastomers and the like. Considering a processability,
polypropylene and the polyolefin base thermoplastic elastomers are
preferred.
[0124] The polypropylene base resins are preferably homogeneous
polypropylene resins, random polypropylene resins, block
polypropylene resins and copolymers having a polypropylene
crystalline part and comprising .alpha.-olefin having 2 to 20
carbon atoms other than propylene. In addition thereto, they
include as well preferably propylene-.alpha.-olefin copolymers
containing 15 mole % or more of a comonomer of ethylene, 1-butene,
4-methyl-1-pentene, 1-hexene or 1-octene.
[0125] The polyolefin base thermoplastic elastomer is preferably an
elastomer obtained by mixing isotactic polypropylene as a hard
segment and atactic polypropylene as a soft segment in a mass ratio
of 80:20.
[0126] The base material of the polyolefin base resin can be
obtained by, for example, a calendar method, an inflation method, a
T die extrusion method and the like.
[0127] A thickness of the base material 2 shall not specifically be
restricted, and it falls in a range of preferably 50 to 150 .mu.m,
more preferably 50 to 120 .mu.m from the viewpoints of a
processability, a flexibility, a strength and the like.
[0128] The base material 2 can be subjected to physical or chemical
surface treatment as is the case with the base material of the
sheet 1.alpha. described above, and a primer layer can be provided
as well. Further, the base material can be colored by using a
pigment and a dye. A coloring mode of the base material sheet
includes transparent coloring and translucent coloring (masking
coloring), and they can be selected according to the applications
thereof.
<Pattern-Printed Layer 3>
[0129] The pattern-printed layer 3 shown in FIGS. 1 and 2 is
provided to endow the sheet 1 of the present invention with a
decorative property, and it comprises preferably a picture layer 3a
and a colored layer 3b. When a color of the base material 2 is used
as it is and does not have to be masked as described later, only
the picture layer 3a may be provided, and on the other hand, when a
pattern is not required, only the colored layer 3b may be
provided.
[0130] The pattern-printed layer 3 can be formed by a publicly
known printing method such as gravure printing, silk screen
printing, offset printing, gravure offset printing, ink jet
printing and the like by using usually an ink.
[0131] The picture layer 3a is provided to endow the base material
2 with a decorative property, and it is formed by printing various
patterns using an ink by means of a printer. The patterns include
woodgrain patterns, pebble patterns imitating a surface of rocks
such as marble patterns (for example, travertine marble patterns),
fabric patterns imitating texture and cloth-like patterns, tiling
patterns, block working patterns and the like, and they include as
well patterns such as marqueteries, patch works and the like which
are obtained by combining the above patterns. These patterns are
formed by polychromic printing using process colors of usual yellow
color, red color, blue color and black color, and in addition
thereto, they are formed as well by polychromic printing using
plates of the respective colors constituting the patterns.
[0132] Inks prepared by suitably mixing a colorant such as a
pigment, a dye and the like, an extender pigment, a solvent, a
stabilizer, a plasticizer, a catalyst, a curing agent and the like
with a binder are used as a picture ink used for the picture layer
3a.
[0133] The binder resin can suitably be selected from publicly
known binders such as thermoplastic resins, thermosetting resins,
ionizing radiation-curable resins and the like according to the
physical properties required and the printing aptitude. Capable of
being used are, for example, single substances or mixtures
comprising cellulose base resins such as nitrocellulose, cellulose
acetate, cellulose acetate propionate and the like; acryl resins
such as polymethyl (meth)acrylate, polybutyl(meth)acrylate,
methyl(meth)acrylate/butyl(meth)acrylate/2-hydroxyethyl(meth)acrylate
copolymers and the like; and in addition thereto, urethane resins,
vinyl chloride-vinyl acetate copolymers, polyester resins, alkyd
resins and the like.
[0134] The above resins can be used alone or in a mixture of two or
more kinds thereof.
[0135] Used as the colorant are inorganic pigments such as carbon
blacks (Japanese inks), iron black, titan white, antimony white,
chrome yellow, titan yellow, iron oxide red, cadmium red,
ultramarine blue, cobalt blue and the like, organic pigments or
dyes such as quinacridone red, isoindolinone yellow, phthalocyanine
blue and the like, metallic pigments comprising flaky foils of
aluminum, brass and the like, pearlescent (pearl) pigments
comprising flaky foils of titanium dioxide-coated mica, basic lead
carbonate and the like.
[0136] The solvent (or dispersant) includes, for example, petroleum
base organic solvents such as hexane, heptane, octane, toluene,
xylene, ethylbenzene, cyclohexane, methylcyclohexane and the like;
ester base organic solvents such as ethyl acetate, butyl acetate,
2-methoxyethyl acetate, 2-ethoxyethyl acetate and the like; alcohol
base organic solvents such as methyl alcohol, ethyl alcohol, normal
propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene
glycol, propylene glycol and the like; ketone base organic solvents
such as acetone, methyl ethyl ketone, methyl isobutyl ketone,
cyclohexanone and the like; ether base organic solvents such as
diethyl ether, dioxane, tetrahydrofuran and the like; chlorine base
organic solvents such as dichloromethane, carbon tetrachloride,
trichloroethylene, tetrachloroethylene and the like; inorganic
solvents such as water and the like. The above solvents (or
dispersants) can be used alone or in a mixture of two or more kinds
thereof.
[0137] Further, a cross-linking agent may be added to the picture
ink. The cross-linking agent includes isocyanate group-containing
compounds, epoxy group-containing compounds, carbodiimide
group-containing compounds, oxazoline group-containing compounds,
silanol group-containing compounds and the like, and the isocyanate
group-containing compounds are preferred.
[0138] The colored layer 3b is usually a uniform and even layer
which coats the base material 2 over a whole surface and which is
provided, if desired, for the purpose of enhancing a designing
property of the sheet 1. It is called as well a masking layer or a
whole solid layer. It is provided to endow a surface of the base
material 2 with a intended color. It is formed usually in a
translucent color in many cases, but it is formed as well in a
colored transparent color in a certain case to use efficiently
patterns which the base material is provided with. Also, in a case
where the white base material 2 is used efficiently and a case
where the base material 2 itself is suitably colored, the colored
layer 3b does not have to be formed.
[0139] The same inks as those used for the picture layer 3a can be
used as the ink used for the colored layer 3b.
<Transparent Resin Layer 4>
[0140] The transparent resin layer 4 shown in FIG. 2 is provided to
protect the pattern-printed layer 3 in the sheet 1 of the present
invention and endow the sheet of the present invention with a
weatherability. The transparent resin layer 4 shall not be
restricted as long as it is transparent and includes any of a
colorless transparent layer, a colored transparent layer and a
translucent layer.
[0141] A layer formed by, for example, a thermoplastic resin can
suitably be used as the transparent resin layer 4. To be specific,
capable of being listed are soft, semi-hard or hard polyvinyl
chloride, polyethylene terephthalate, polybutylene terephthalate,
polyamide, polyethylene, polypropylene, ethylene/vinyl acetate
copolymers, ethylene/acrylic acid copolymers, ethylene acrylic
ester copolymers, ionomers, acrylic esters, methacrylic esters and
the like. In the present invention, polyolefin base resins such as
polypropylene and the like are particularly preferred for the
transparent resin layer 4.
[0142] The transparent resin layer 4 may be colored if necessary.
In this case, a colorant (pigment or dye) can be added to the above
thermoplastic resins to color them. Publicly known or commercially
available pigments or dyes can suitably be used as the colorant. At
least one or two or more kinds thereof can be selected. Also, an
addition amount of the colorant can suitably be set according to
the desired colors.
[0143] Further, a UV absorber (UVA) and a light stabilizer are
preferably added as a weatherability-improving agent to the
transparent resin layer 4. The UV absorber (UVA) absorbs a harmful
UV ray to enhance a long term weatherability and a stability of the
decorated sheet of the present invention. Also, the light
stabilizer (HALS) in itself hardly absorbs a UV ray but scavenges
efficiently harmful free radicals generated by a UV ray energy to
thereby stabilize the decorated sheet.
[0144] The UV absorber may be any of inorganic absorbers and
organic absorbers, and titanium oxide, cerium oxide, zinc oxide and
the like which have an average particle diameter of 5 to 120 nm can
preferably be used as the inorganic UV absorber. Also, UV absorbers
of a benzotriazole base, a triazine base, a benzophenone base, a
salicylate base, an acrylonitrile base and the like can preferably
be listed as the organic UV absorber. Among them, the triazine base
UV absorbers which have a high UV ray-absorbing ability and which
are less liable to be degraded by a high energy such as a UV ray
and the like are more preferred. The triazine base UV absorbers
include preferably those used for the coating composition of the
present invention described above.
[0145] The light stabilizer includes preferably such the foregoing
hindered amine base light stabilizers (HALS) as contained in the
coating composition.
[0146] Also, reactive UV absorbers and light stabilizers each
having a polymerizable group such as a (meth)acryloyl group and the
like in a molecule can also be used as the UV absorber and the
light stabilizer.
[0147] A content of the UV absorber in the transparent resin layer
4 falls in a range of usually 0.1 to 1 part by mass, preferably 0.3
to 0.8 part by mass based on 100 parts by mass of the resin
constituting the transparent resin layer 4. If it is 0.1 part by
mass or more, the decorated sheet of the present invention can be
provided with a sufficiently high weatherability, and if it is 1
part by mass or less, bleeding out is not brought about.
[0148] A content of the light stabilizer in the transparent resin
layer 4 falls in a range of usually 0.05 to 0.8 part by mass,
preferably 0.1 to 0.5 part by mass based on 100 parts by mass of
the resin constituting the transparent resin layer 4. If it is 0.05
part by mass or more, the decorated sheet of the present invention
can be provided with a sufficiently high weatherability, and if it
is 0.8 part by mass or less, bleeding out is not brought about.
[0149] Also, various additives such as a filler, a delusterant
(matting agent), a flame retardant, a lubricant, an antistatic
agent, an antioxidant, a soft component (for example, rubber) and
the like may be contained in the transparent resin layer 4.
[0150] A method for forming the transparent resin layer 4 shall not
specifically be restricted, and various methods can be used.
Capable of being employed is, for example, any of a method in which
a sheet or film formed in advance is laminated on an adjacent
layer, a method in which a resin composition capable of forming the
transparent resin layer 4 is molten and extruded to thereby coat it
on an adjacent layer and a method in which the transparent resin
layer 4 is laminated together with an adjacent layer.
[0151] In the present invention, the transparent resin layer 4 is
formed preferably by melt extrusion, and the transparent resin
layer 4 is coated preferably by melting and extruding a polyolefin
base resin. To be specific, the adhesive layer 8 is formed in
advance on the pattern-printed layer 3, and a polypropylene base
thermoplastic elastomer is coated on the above adhesive layer 8 by
melting and extruding, whereby the transparent resin layer 4 can
suitably be formed. A method for melting and extruding can be
carried out according to, for example, a publicly known method
using a T die.
[0152] A thickness of the transparent resin layer 4 can suitably be
set according to the applications and the use method of the
finished product, and usually it is preferably 20 to 250 .mu.m,
particularly preferably 50 to 200 .mu.m.
Transparent Resin Layer Concave Part:
[0153] The transparent resin layer 4 may have concave parts as
shown in FIG. 1. A method for providing the transparent resin layer
4 with the concave parts shall not specifically be restricted, and
they are provided by, for example, emboss processing. The emboss
processing may be carried out by a usual method using a publicly
known embossing equipment of a single layer type or a rotary type,
and in addition thereto, it may be carried out as well by a method
(so-called doubling emboss method) in which the emboss processing
is carried out at the same time in a step of laminating the
transparent resin layer 4 on the pattern-printed layer 3.
[0154] A surface (front surface) and/or a rear surface of the
transparent resin layer 4 can be subjected, if necessary, to corona
discharge treatment in order to enhance an adhesive property with
an adjacent layer. The method and the conditions of the corona
discharge treatment can conformed to those of a publicly known
method.
<Colored Resin Layer 9>
[0155] It is preferred in terms of enhancing the designing property
and the weatherability that the concave parts provided on the
transparent resin layer 4 described above are subjected to wiping
processing to form a colored resin layer 9. The wiping processing
means processing in which a colored ink composition is filled into
the concave parts provided by the emboss processing while wiping a
surface thereof by a doctor blade.
[0156] The colored ink composition is obtained preferably by
dissolving (or dispersing) a publicly known colorant (dye or
pigment) in a solvent (or a dispersant) together with polycarbonate
base urethane (meth)acrylate, polyester base urethane
(meth)acrylate or a resin comprising polycarbonate base urethane
(meth)acrylate and (meth)acryl polyol which is a binder resin. The
same colorant and solvent as those described above in the
pattern-printed layer can be used for the colorant and the solvent
contained in the colored ink composition.
[0157] The polycarbonate base urethane (meth)acrylate described
above as the binder resin is a resin obtained by radically
polymerizing a (meth)acryl monomer using as a radical
polymerization initiator, a polycarbonate base polyurethane high
polymer obtained by reacting polycarbonatediol with
diisocyanate.
[0158] In this respect, the diisocyanate includes aromatic
isocyanates, aliphatic isocyanates, alicyclic isocyanates and
adducts and polymers thereof, and they can be used alone or in
combination of two or more kinds thereof. Among them, preferred are
aliphatic isocyanates such as hexamethylenediisocyanate and the
like and alicyclic isocyanates such as isophoronediisocyanate,
hydrogenated xylylenediisocyanate and the like.
[0159] The acryl monomer includes preferably (meth)acrylic acid and
alkyl(meth)acrylates in which an alkyl group has 1 to 6 carbon
atoms, and they can be used alone or in combination of two or more
kinds thereof.
[0160] A mass ratio of a (meth)acryl component and a urethane
component in the polycarbonate base urethane (meth)acrylate shall
not specifically be restricted, and a mass ratio of the urethane
component:the (meth)acryl component falls in a range of preferably
80:20 to 20:80, more preferably 70:30 to 30:70 in terms of the
weatherability and the solvent resistance. If the contents of the
acryl component and the urethane component fall in the ranges
described above, the excessively hard coating film is prevented
from being formed, and the sufficiently high processing aptitude is
obtained. The problem that white lines (whitening) are produced on
a surface of the resin in bending processing is not brought
about.
[0161] The ester base urethane (meth)acrylate is a resin obtained
by radically polymerizing a (meth)acryl monomer using as a radical
polymerization initiator, a polyester base polyurethane high
polymer obtained by reacting polyesterdiol with diisocyanate. The
diisocyanate and the (meth)acryl monomer are suitably selected from
those used for the polymerization of the polycarbonate base
urethane (meth)acrylate described above.
[0162] An acryl polyol is obtained by introducing a hydroxyl group
into the (meth)acryl monomer described above. It can be
synthesized, for example, by copolymerizing the (meth)acryl monomer
described above with hydroxy(meth)acrylate such as
2-hydroxyethyl(meth)acrylate, 2-hydroxy-3-phenoxypropyl
(meth)acrylate and the like. These (met)acryl polyols play a
function of a cross-linking agent.
[0163] A mass ratio of the polycarbonate base urethane
(meth)acrylate to the (meth)acryl monomer falls in a range of
preferably 100:0 in which the polycarbonate base urethane
(meth)acrylate is used alone to 10:90, more preferably 100:0 to
30:70. If it falls in the above ranges, the sufficiently high
weatherability is obtained. If the polycarbonate base urethane
(meth)acrylate is used alone, not only the weatherability is
reduced, but also since this is reacted with isocyanate, an
adhesive property thereof with the ionizing radiation-curable resin
is changed with the passage of time, and the stable performances
are not exerted in a certain case.
[0164] The colored resin layer 9 is formed, as described above, by
introducing the ink composition into the concave parts of the
transparent resin layer 4. The designing effect is enhanced by a
synergistic effect of the colored resin layer 9 formed in the
concave parts and the pattern-printed layer 3. In particular, a
design closer to an actual wood grain can be expressed by forming
the colored resin layer in the concave parts of wood grain conduit
groove irregularities, and this can enhance the commercial value.
Further, the UV absorber (UVA) and the light stabilizer (HALS) are
added, as described above, to the ink composition used for wiping
processing, whereby the colored resin layer 9 can be provided with
a weatherability.
<Adhesive Layer 8>
[0165] The adhesive layer 8 has a function to even out
irregularities formed by the pattern-printed layer 3 and enhance an
adhesive property of the transparent resin layer 4 with the base
material 2, and it comprises a transparent layer.
[0166] An ink prepared by suitably mixing a binder with, if
necessary, an extender filler, a solvent, a stabilizing agent, a
plasticizer, a catalyst, a UV absorber, a light stabilizer, a
curing agent and the like is used as the ink for forming the
adhesive layer 8. The above binder shall not specifically be
restricted, and acryl/polyurethane base copolymers are preferred
since they are provided with a flexibility, a toughness and an
elasticity in combination. Considering the environment, resins
containing chlorine are preferably not used.
[0167] A coating amount of the adhesive layer 8 falls in a range of
preferably 2 to 25 g/m.sup.2. If it is 2 g/m.sup.2 or more, a
sufficiently high adhesive property of the base material 2 with the
transparent resin layer 4 is obtained, and if it is 25 g/m.sup.2 or
less, it is preferred from an economical viewpoint. From the above
viewpoints, a coating amount of the above ink falls usually, though
depending on the kind of the base material 4, in a range of more
preferably 3 to 20 g/m.sup.2.
[0168] Also, a thickness of the adhesive layer 8 falls in a range
of usually 2 to 25 .mu.m, preferably 3 to 20 .mu.m.
<Primer Layer 5>
[0169] In the sheet 1.beta. of the present invention, a primer
layer 5 is laminated preferably on the transparent resin layer
4.
[0170] A resin suitably selected from the binder resins used for
the ink composition forming the colored resin layer 9 described
above is preferably used for the primer layer 5. That is,
polycarbonate base urethane (meth)acrylate, polyester base urethane
(meth)acrylate or a resin comprising polycarbonate base urethane
(meth)acrylate and (meth)acryl polyol is preferably used therefor.
Use of the above resins makes it possible to provide the sheet 113
of the present invention with a very high weatherability.
[0171] The same weatherability-improving agent as used in the
transparent resin layer 4 is preferably added to the primer layer 5
described above in order to enhance further the weatherability, and
a UV absorber (UVA) and a light stabilizer (HALS) are preferably
added. A content of the UV absorber is preferably 0.1 to 25 parts
by mass, more preferably 1 to 25 parts by mass, further preferably
3 to 20 parts by mass and particularly preferably 5 to 20 parts by
mass based on 100 parts by mass of the resin forming the primer
layer 5. Also, a content of the light stabilizer is preferably 0.05
to 7 parts by mass, more preferably 0.5 to 5 parts by mass, further
preferably 1 to 5 parts by mass and particularly preferably 2 to 5
parts by mass based on 100 parts by mass of the resin forming the
primer layer 5.
[0172] A thickness of the primer layer 5 shall not specifically be
restricted as long as it falls in a range in which the effects of
the present invention are exerted, and it falls in a range of
preferably 0.5 to 10 .mu.m, more preferably 1 to 5 .mu.m from the
viewpoint of obtaining the sufficiently high weatherability.
[0173] The primer layer can be formed by publicly known printing
methods, coating methods and the like using the resin composition
described above as it is or in a state in which it is dissolved or
dispersed in a solvent. Also, the primer layer may assume an
embodiment in which it is provided with irregularities as shown in
FIG. 2 or an embodiment in which it is even and provided with no
irregularities. The embodiment in which the primer layer is
provided with irregularities is preferred from the viewpoint of
enhancing the designing property.
<Surface Protective Layer 6>
[0174] The sheet 1.beta. of the present invention has a surface
protective layer 6 on an outermost surface. The above surface
protective layer 6 is the same as the surface protective layer of
the foregoing sheet 1.alpha. in the present invention. Also, the
surface protective layer 6 has preferably concave parts from the
viewpoint of enhancing the designing property. A method for
providing the surface protective layer 6 with the concave parts is
also the same as in the surface protective layer of the sheet
1.alpha. in the present invention.
[0175] The primer layer 6 may assume an embodiment in which it is
provided with irregularities as shown in FIG. 2 or an embodiment in
which it is even and provided with no irregularities. The
embodiment in which the primer layer is provided with
irregularities is preferred from the viewpoint of enhancing the
designing property. Also, concave parts may be provided, as shown
in FIG. 3, on a surface protective layer which is even and provided
with no irregularities. In the above case, the same method as that
used in providing the concave parts on the transparent resin layer
4 can be used as a method for forming the above concave parts.
<<Decorated Sheet>>
[0176] The sheet 1 of the present invention can be used as a
decorated sheet by laminating on an adherend so that the surface
protective layer of the above sheet 1 is an outermost surface. Any
of the sheet 1 and the sheet each described above can be employed
for the decorated sheet, and the sheet is preferably laminated from
the viewpoint of a designing property.
<Adherend>
[0177] The adherend shall not specifically be restricted, and the
same ones as those used for publicly known decorated sheets can be
used. They include, for example, woody materials, metals, ceramics,
plastics, glasses and the like. In particular, the sheet 1 of the
present invention can suitably be used for metal materials such as
steel plates and the like and woody materials. The steel plates
include, to be specific, hot dip galvanized sheet iron and the
like, and the woody materials include, to be specific, wood
veneers, lumber single panels, lumber plywoods, particle boards,
middle density fiberboards (MDF) and the like which are produced
from various materials such as Japanese cedar, cypress, zelkova
tree, pine tree, lauan, teak, melapi and the like.
[0178] A method for laminating the sheet 1 of the present invention
on various adherends shall not specifically be restricted, and a
method in which the sheet 1 is adhered on an adherend by an
adhesive can be employed. The adhesive can suitably be selected
from publicly known adhesives according to the kind of the
adherends. It includes, for example, polyvinyl acetate, polyvinyl
chloride, polyvinyl chloride/polyvinyl acetate copolymers,
ethylene/acrylic acid copolymers, ionomers and the like, and in
addition thereto, it includes butadiene/acrylonitrile rubbers,
neoprene rubbers natural rubbers and the like.
[0179] In adhering the sheet 1 of the present invention on various
adherend by an adhesive, a rear face primer layer 7 is preferably
provided since the adhesive property can be enhanced.
[0180] The decorated sheet thus produced can preferably be used,
for example, as interior materials such as walls, ceilings, floors
and the like, surface decorative sheets of fittings such as window
frames, doors, handrails and the like, surface decorative sheets
for cabinets of furnitures or light electric and OA appliances and
exterior materials for front doors and the like. In particular, the
decorated sheet prepared by using the sheet 1 of the present
invention is excellent in a weatherability and has a high
processing aptitude, and therefore it is stuck on a steel plate and
suitably used as an exterior material for an entrance and the
like.
Sheet 2:
[0181] A second embodiment of the sheet of the present invention
(hereinafter referred to merely as the "sheet 2") has a surface
protective layer which is obtained by cross-linking and curing the
coating composition 2, and it shall not specifically be restricted
as long as it has the above surface protective layer. The preferred
embodiment of the sheet 2 of the present invention is the
embodiments shown in FIGS. 1 and 2, that is, the same embodiments
as those of the sheet 1.alpha. and the sheet 1.beta..
[0182] Also, the sheet 2 of the present invention can be laminated
on an adherend to prepare a decorated sheet. A constitution of the
above decorated sheet is the same as that of the decorated sheet
explained in the first embodiment of the sheet of the present
invention.
Sheet 3:
[0183] A third embodiment of the sheet of the present invention
(hereinafter referred to merely as the "sheet 3") has a surface
protective layer which is obtained by cross-linking and curing the
coating composition 3, and it shall not specifically be restricted
as long as it has the above surface protective layer. FIG. 4 is a
schematic drawing showing a cross section of the preferred
embodiment of the sheet 3 in the present invention. In the
embodiment shown in FIG. 4, a primer layer 4 and a surface
protective layer 6 are laminated in order on one face of a base
material 2.
<<Base Material>>
[0184] Materials used as the base material 2 in the sheet 3 of the
present invention are preferably plastic films and plastic sheets,
and they include preferably materials comprising polyolefin resins,
vinyl base resins, polyester resins, acryl resins, polyamide
resins, cellulose base resins, polystyrene resins, polycarbonate
resins, polyallylate resins, polyimide resins and the like.
Considering a visible light transmission property and a
workability, among them, preferred are base material films of
polyolefin resins such as polyethylene, polypropylene, polybutene,
polymethylpentene, ethylene/propylene copolymers,
ethylene/propylene/butene copolymers, polyolefin base thermoplastic
elastomers and the like, and polyethylene and polypropylene are
more preferred.
<UV Absorber>
[0185] The base material 2 used in the sheet 3 of the present
invention contains preferably a UV absorber for the purpose of
enhancing a weatherability. The UV absorber shall not specifically
be restricted and includes preferably, for example, UV absorbers of
a triazine base, a benzotriazole base, a benzophenone base, a
benzoate base, a benzoic acid base, a salicylic acid base, a
malonic acid base, an oxanilide base, oxalamide base and the
like.
[0186] A content of the UV absorber contained in the base material
2 is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 3
parts by mass based on 100 parts by mass of the resin used for the
base material 2. If a content of the UV absorber falls in the
ranges described above, the sheet 3 of the present invention can be
efficiently provided with an excellent weatherability.
<Antistatic Agent>
[0187] The base material 2 contains preferably an antistatic agent
from the viewpoint of providing the sheet 3 of the present with a
self-cleaning performance and a visible light transmission
property. The antistatic agent includes preferably high polymer
type antistatic agents having a polyether structure such as
polyether/polyolefin copolymers, polyetherester,
polyetheresteramide, polyetheramide, polyetheramideimide and the
like. They can be used alone or in combination of plural kinds
thereof. Among them, the polyether/polyolefin copolymers and the
polyetheresteramide are more preferred.
[0188] In this regard, the polyether/polyolefin copolymers include
block copolymers in which a polyether part formed by polyethylene
glycol and polypropylene glycol and a polyolefin part formed by
polyethylene and polypropylene are combined alternately and in
addition thereto, random copolymers and graft copolymers, and they
are preferably the block copolymers from the viewpoint of providing
a self-cleaning property. Commercially available products can be
used as well for the above antistatic agents. The antistatic agents
of the polyether/polyolefin copolymer include, for example,
commercially available products such as "Pelestat 300", "Pelestat
230", "Pelestat 303" and the like, and the antistatic agents of the
polyetheresteramide include commercially available products such as
"Pelestat 6321" and the like.
[0189] A content of the antistatic agent contained in the base
material 2 is 5 to 30 parts by mass, preferably 10 to 20 parts by
mass based on 100 parts by mass of the resin used for the base
material 2. If a content of the antistatic agent falls in the
ranges described above, the sheet 3 of the present invention can be
efficiently provided with an excellent weatherability and an
excellent visible light transmission property.
[0190] The base material 2 can be subjected, if desired, on one
face or both faces to physical or chemical treatment including an
oxidation method such as corona discharge treatment, chromium
oxidation treatment, hot blast treatment, an ozone.cndot.UV ray
treating method and the like and a roughening method such as a sand
blast method, a solvent treating method and the like.
[0191] A thickness of the base material film shall not specifically
be restricted, and securing an excellent weatherability and
considering a workability and a general versatility, it falls in a
range of usually 20 to 200 .mu.m, preferably 30 to 150 .mu.m.
[0192] In the sheet 3 of the present invention, the base material 2
is prepared by turning the mixture obtained by mixing the resin,
the UV absorber, the antistatic agent and the like each described
above into film by, for example, a calendar method, an inflation
method, a T die extrusion method and the like and more preferably
biaxially stretching the film
<<Primer Layer>>
[0193] The base material 2 is subjected preferably to such
treatment as forming a primer layer 4 for strengthening an
interlayer adhesive property between the above base material 2 and
a surface protective layer 6. A material used for forming the
primer layer 4 shall not specifically be restricted and includes
acryl base resins, vinyl chloride/vinyl acetate copolymers,
polyesters, polyurethanes, urethane acryl base resins, chlorinated
polypropylene, chlorinated polyethylene and the like.
[0194] Further, the material used for forming the primer layer 4
includes preferably polycarbonate base urethane/acryl copolymers,
polyester base urethane/acryl copolymers or resins comprising
polycarbonate base urethane acryl and acryl or acryl polyol.
[0195] In this regard, the polycarbonate base urethane/acryl
copolymer is a resin obtained by radically polymerizing an acryl
monomer with a polycarbonate base polyurethane polymer obtained by
reacting polycarbonatediol with diisocyanate using a radical
polymerization initiator. Also, the polyester base urethane/acryl
copolymer is a resin obtained by radically polymerizing an acryl
monomer with a polyester base polyurethane polymer obtained by
reacting polyesterdiol with diisocyanate using a radical
polymerization initiator.
[0196] A UV absorber and a light stabilizer which are used for the
primer layer can be added as well to the primer layer 4, and
therefore it can be provided with an excellent weatherability by
the sheet 3 of the present invention. A content of the UV absorber
is preferably 5 to 40 parts by mass, more preferably 5 to 30 parts
by mass and further preferably 5 to 25 parts by mass based on 100
parts by mass of the resin used for forming the primer layer 4.
Also, a content of the light stabilizer is preferably 5 to 40 parts
by mass, more preferably 5 to 30 parts by mass and further
preferably 5 to 20 parts by mass based on 100 parts by mass of the
resin used for forming the primer layer 4.
[0197] Further, painting for adjusting the color and patterns from
the viewpoint of the design may be formed in advance as long as the
visible light transmission property is not inhibited.
<<Surface Protective Layer>>
[0198] The surface protective layer 6 is a layer obtained by
cross-linking and curing the coating composition 3 of the present
invention described above. A thickness of the surface protective
layer 6 is preferably 3 to 20 .mu.m, more preferably 3 to 15 .mu.m
and further preferably 5 to 12 .mu.m. If a thickness of the surface
protective layer 6 falls in the ranges described above, the
excellent self-cleaning performance, the excellent visible light
transmission property and the excellent light fastness can
efficiently be obtained. Further, the excellent workability is
obtained as well.
<<Rear Face Coating Layer>>
[0199] The sheet 3 of the present invention can be provided with a
rear face coating layer (not illustrated) on a surface opposite to
a surface of the base material 2 on which the surface protective
layer 6 described above is provide. The rear face coating layer can
be endowed with performances according to the applications of the
sheet 3 of the present invention. The same layer as the surface
protective layer 6 described above can be provide, and a layer
having different performances from those of the above surface
protective layer 6 can be provided as well.
[0200] When the sheet 3 of the present invention is used for an
agricultural film, the rear face coating layer is preferably a
layer containing a drip-proof agent.
<Drip-Proof Agent>
[0201] Drip-proof agents which are usually used can be used for a
drip-proof agent used for the sheet 3 of the present invention
without limits. It includes preferably, for example, surfactants
such as nonionic surfactants, anionic surfactants, cationic
surfactants, amphoteric surfactants and the like and in addition
thereto, particles of inorganic compounds such as silica, alumina,
titanium oxide and the like, and the drip-proof agents of the
inorganic compounds are preferably used from the viewpoint of a
drip-proof property, especially a persistence of a drip-proof
property.
[0202] In the sheet 3 of the present invention, among the inorganic
compounds described above, silica particles are preferred, and
silica particles having an average primary particle diameter of 1
to 300 nm, preferably 1 to 200 nm and more preferably 1 to 50 nm
are preferred. A persistence of the particularly excellent droplet
flow property is obtained by using the silica particles having the
average primary particle diameters described above.
[0203] Any of polyhydric alcohol type surfactants and polyethylene
glycol type surfactants can be used as the nonionic surfactants. To
be specific, the polyhydric alcohol type surfactants include
stearic acid sorbitan esters and oleic acid sorbitan esters of
sorbitan mono-fatty acid esters, and the polyethylene glycol type
surfactants include polyoxyethylene oleic acid esters,
polyoxyethylene oleic acid diesters, polyoxyethylene stearic acid
esters and the like.
[0204] The anionic surfactants include polyoxyethylene lauryl ether
sodium sulfate of sulfuric ester salts, sodium
alkylnaphthalenesulfonate of sulfonic acid salts, potassium
alkylphosphate of phosphoric ester salts and the like, and the
cationic surfactants include primary to tertiary amine salts,
quaternary ammonium salts and the like. The amphoteric surfactants
include amino acid type amphoteric surfactants, betaine type
amphoteric surfactants and the like.
[0205] Also, surfactants having a reactivity can preferably be used
as well for the surfactants. The surfactants having a reactivity
include surfactants having functional groups having ethylenically
double bonds such as a (meth)acryloyl group, a vinyl group, an aryl
group and the like.
[0206] The rear face coating layer is formed by a coating
composition for a rear face containing the drip-proof agent and a
binder resin described later which form the above rear face coating
layer, and a content of the drip-proof agent in the rear face
coating layer is preferably 5/95 to 60/40, more preferably 5/95 to
55/45 and further preferably 5/95 to 30/70 in terms of a blend mass
ratio of the binder resin to the drip-proof agent. If a content of
the drip-proof agent falls in the ranges described above, an effect
of the excellent drip-proof property is efficiently obtained, and
whitening is not brought about on the rear face coating layer.
Further, the plural sheets are readily connected by heat fusion,
that is, the processability is enhanced.
<Binder Resin>
[0207] The rear face coating layer is formed usually by coating the
coating composition for a rear face containing the drip-proof agent
and the binder resin and curing it. The binder resin can suitably
be selected from publicly known binders such as thermoplastic
resins, thermosetting resins and the like, and it includes
preferably, for example, single substances or mixtures comprising
cellulose base resins such as nitrocellulose, cellulose acetate,
cellulose acetate propionate and the like; acryl resins such as
polymethyl (meth)acrylate, polybutyl(meth)acrylate, methyl
(meth)acrylate/butyl(meth)acrylate/2-hydroxyethyl (meth)acrylate
copolymers and the like; and in addition thereto, urethane resins,
vinyl chloride/vinyl acetate copolymers, polyester resins, alkyd
resins and the like. The above resins can be used alone or in a
mixture of two or more kinds thereof.
[0208] The binder resin includes preferably ionizing
radiation-curable resins. If the ionizing radiation-curable resin
is used, the excellent drip-proof property is obtained, and
particularly a persistence thereof is excellent. Further, the
excellent processability is obtained as well. The ionizing
radiation-curable resin used for the rear face coating layer
includes preferably the polymerizable oligomers described as the
ionizing radiation-curable resin which can be used for forming the
surface protective layer described above, that is, the oligomers
having a radically polymerizable unsaturated group in a molecule
such as the oligomers of an epoxy (meth)acrylate base, a urethane
(meth)acrylate base, polyether base urethane (meth)acrylate, a
polyester (meth)acrylate base and a polyether (meth)acrylate base.
Among them, the oligomers of the urethane (meth)acrylate base are
preferred. The above urethane (meth)acrylate base oligomers can be
obtained, for example, by esterifying polyurethane oligomers
obtained by reacting polyetherpolyol and polyesterpolyol with
polyisocyanate by (meth)acrylic acid.
[0209] The number of the functional groups in the urethane
(meth)acrylate which is employed as the ionizing radiation-curable
resin used for the rear face coating layer is preferably 2 to 16,
more preferably 2 to 10 and further preferably 2 to 6. If the
number of the functional groups falls in the ranges described
above, the drip-proof property and particularly a persistence
thereof are excellent, and the excellent processability is obtained
as well.
<Various Additives>
[0210] A rear face coating composition forming the rear face
coating layer can contain various additives as long as a drip-proof
property which is a preferred important performance of the rear
face coating layer is not inhibited. The various additives include,
in addition to, for example, the UV absorber contained in the
surface protective layer, a polymerization inhibitor, a
cross-linking agent, an antistatic agent, an adhesion improving
agent, an antioxidant, a leveling agent, a thixotropy-providing
agent, a coupling agent, a plasticizer, a defoaming agent, a
filler, a solvent and the like.
[0211] A thickness of the rear face coating layer is preferably 0.3
to 10 .mu.m, more preferably 0.3 to 5 .mu.m and further preferably
0.5 to 4 .mu.m. If a thickness of the rear face coating layer falls
in the ranges described above, the excellent drip-proof property is
efficiently obtained, and the excellent processability is obtained
as well.
<<Production Method for the Sheet 3>>
[0212] The sheet 3 of the present invention can more preferably be
produced, for example, by the following method. The resin
composition for forming the primer layer preferably provided is
coated on one face of the base material 2, and then the coating
composition 3 forming the surface protective layer 6 is coated
thereon. In this respect, the resin composition for forming the
primer layer and the coating composition 3 are coated by publicly
known methods such as gravure coating, bar coating, roll coating,
reverse roll coating, comma coating and the like, preferably
gravure coating so that the respective thicknesses thereof after
curing fall in the ranges described above.
[0213] An uncured resin layer formed by coating the coating
composition 3 is cross-linked and cured by irradiating with an
ionizing radiation such as an electron beam, a UV ray and the like,
whereby it is turned into the surface protective layer 6. A method
for cross-linking and curing the above uncured resin layer is the
same as the method for cross-linking and curing in the surface
protective layer of the sheet 1 in the first embodiment of the
sheet of the present invention.
[0214] Also, when the rear face coating layer is provided, the
coating composition for a rear face which forms the rear face
coating layer is coated on a surface opposite to a surface of the
base material 2 on which the surface protective layer 6 is provide
before or after coating the ionizing radiation-curable resin
composition used for forming the surface protective layer 6.
[0215] The uncured resin layer formed by coating the coating
composition for a rear face in forming the rear face coating layer
is different in a curing method depending on the binder resin used
for the above coating composition, and when a thermosetting resin
and a thermoplastic resin are employed, the uncured resin layer is
cured by heat treatment to obtain the rear face coating layer.
Also, when the ionizing radiation-curable resin is employed as the
binder resin, the uncured resin layer is cured in the same manner
as in the coating composition 3 used for forming the surface
protective layer 6 to obtain the rear face coating layer. The order
of forming the surface protective layer 6 shall not specifically be
restricted, and the rear face coating layer can be formed usually
after forming the surface protective layer 6 by cross-linking and
curing.
[0216] The sheet 3 thus obtained is provided with an excellent
self-cleaning property and an excellent weatherability and in
addition thereto, a visible light transmission property, a UV
ray-blocking performance, a weatherability-keeping property, a
workability and a persistence thereof, and therefore it is suitably
used for applications such as agricultural use for plastic houses
and the like and protective sheets for plate glasses. Also, when
the rear face coating layer is provided, the sheet has a drip-proof
property, and therefore it is more suitably used for applications
such as agricultural use for plastic houses and protective sheets
for plate glasses.
[0217] When the sheet 3 of the present invention is used for
agricultural use such as plastic houses and the like, it is
provided preferably with the surface protective layer 6 turned to
an outside (an outside of the plastic houses). It becomes possible
to put effectively the characteristics of the surface protective
layer 6 to efficient use, and the sheet is provided with an
excellent performance as an agricultural film.
Sheet 4:
[0218] A fourth embodiment of the sheet of the present invention
(hereinafter referred to merely as the "sheet 4") has a surface
protective layer obtained by cross-liking and curing a coating
composition 4, and it shall not specifically be restricted as long
as it has the above surface protective layer. A specific layer
constitution of the sheet 4 includes, for example:
(1) a constitution in which a surface protective layer is laminated
on a base material, (2) a constitution in which a primer layer and
a surface protective layer are laminated in order on a base
material, (3) a constitution in which a pattern-printed layer, a
primer layer and a surface protective layer are laminated in order
on a base material, (4) a constitution in which a transparent resin
layer, a primer layer and a surface protective layer are laminated
in order on a base material, (5) a constitution in which a
transparent adhesive layer, a transparent resin layer, a primer
layer and a surface protective layer are laminated in order on a
base material and (6) a constitution in which a pattern-printed
layer, a transparent adhesive layer, a transparent resin layer, a
primer layer and a surface protective layer are laminated in order
on a base material. The layer constitution of (6) described above
shall be shown below and explained as an example for explanation of
the specific layer constitution.
[0219] The base material and the pattern-printed layer (the picture
layer and the colored layer) are the same as those of the sheet 1.
Also, the surface protective layer is the same as that of the sheet
1, except that the coating composition 4 of the present invention
is used.
<<Primer Layer>>
[0220] The primer layer can be formed by coating a publicly known
primer agent on one face or both faces of the base material. The
primer agent includes, for example, urethane resin base primer
agents comprising acryl-modified urethane resins and the like,
primer agents comprising urethane/cellulose base resins (for
example, resins obtained by adding hexamethylenediisocyanate to a
mixture of urethane and nitrocellulose) and the like.
[0221] A coating amount of the primer agent shall not specifically
be restricted, and it is usually 0.1 to 20 g/m.sup.2, preferably
0.5 to 10 g/m.sup.2.
<<Transparent Adhesive Layer>>
[0222] The transparent adhesive layer is a layer provided on the
pattern-printed layer. The transparent adhesive layer shall not
specifically be restricted as long as it is a transparent layer,
and it includes any of the clear and colorless, colored transparent
and translucent layers. The transparent adhesive layer is formed in
order to adhere the pattern-printed layer with the transparent
resin layer.
[0223] The adhesive shall not specifically be restricted, and
adhesives which are publicly known in the field of a decorated
sheet can be used. The above adhesives include, for example,
thermoplastic resins such as polyamide resins, acryl resins, vinyl
acetate resins and the like and thermosetting resins such as
thermosetting urethane resins and the like. Further, two-component
curing type polyurethane resins or polyester resins using
isocyanate as a curing agent can be applied as well.
[0224] The transparent adhesive layer can be formed, for example,
by coating the adhesive on the pattern-printed layer (to be strict,
on the base material so that the picture layer is covered), coating
the coating agent constituting the transparent resin layer and then
drying and curing it. The conditions of the drying temperature, the
drying time and the like shall not specifically be restricted, and
they can suitably be set according to the kind of the adhesives. A
method for coating the adhesive shall not specifically be
restricted, and capable of being employed are methods such as roll
coating, curtain flow coating, wire bar coating, reverse coating,
gravure coating, gravure reverse coating, air knife coating, kiss
coating, blade coating, smooth coating, comma coating and the
like.
[0225] A thickness of the transparent adhesive layer shall not
specifically be restricted, and a thickness thereof after dried is
0.1 to 30 .mu.m, preferably 1 to 20 .mu.m.
<<Transparent Resin Layer>>
[0226] The transparent resin layer may be colored as long as it is
transparent, and it may be translucent as long as the
pattern-printed layer is visible.
[0227] The resin constituting the transparent resin layer includes,
for example, polyvinyl chloride, polyethylene terephthalate,
polybutylene terephthalate, polyamide, polyethylene, polypropylene,
ethylene/vinyl acetate copolymers, ethylene/acrylic acid
copolymers, ethylene/acrylic ester copolymers, ionomers,
polymethylpentene, (meth)acrylic esters, polycarbonate, cellulose
triacetate and the like. Among the resins described above,
polyolefin base resins such as polypropylene and the like are
preferred. Polyolefin base resins having a stereoregularity are
more preferred. When the polyolefin base resin is used, the
transparent resin layer is preferably formed from the molten
polyolefin base resin by an extrusion method.
[0228] Various additives such as a filler, a delusterant, a foaming
agent, a flame retardant, a lubricant, an antistatic agent, an
antioxidant, a UV absorber, a light stabilizer, a radical
scavenger, a soft component (for example, rubber) and the like may
be contained, if necessary, in the transparent resin layer.
[0229] A thickness of the transparent resin layer shall not
specifically be restricted, and it is set usually to 10 to 150
.mu.m.
[0230] A face which is a surface of the transparent resin layer and
on which the surface protective layer is formed may be subjected,
if necessary, to surface treatment such as corona discharge
treatment, ozone treatment, plasma treatment, ionizing radiation
treatment, bichromic acid treatment and the like. The surface
treatment can be carried out according to the conventional methods
of the respective treatments.
<<Emboss Processing>>
[0231] After the coating composition 4 of the present invention is
laminated as the surface protective layer (outermost surface layer)
on the transparent resin layer described above, a front face of the
surface protective layer may be subjected to emboss processing.
[0232] An emboss processing method therefor shall not specifically
be restricted, and it can be carried out by a usual method using a
publicly known embossing equipment of a single layer type or a
rotary type. An irregularity form thereof includes, for example,
wood grain conduit groove, stone slab surface irregularity (granite
peeled face and the like), cloth surface texture, pearskin finish,
sand grain, hair line, line screen groove and the like.
[0233] Alkyl silicate having a methoxy group is contained in the
sheet 4 of the present invention, and therefore when the above
sheet is brought into contact with water (rain water), a hydroxyl
group is produced by hydrolysis of the alkyl silicate to provide
the sheet with a hydrophilicity. In this regard, the alkyl silicate
having a methoxy group is used in the present invention, and
therefore the hydrophilicity is obtained more quickly than in a
case in which other alkyl silicates (for example, alkyl silicates
having ethyl and butyl) are used.
[0234] Development of the hydrophilicity allows a wetting property
of water to be enhanced and a self-cleaning action of the sheet 4
to be exerted. That is, contaminants of the sheet 4 are liable to
be removed by rain water and the like, and the contaminants are
less liable to be deposited thereon. Further, a thin water film is
liable to be formed on a whole part of the sheet 4 by rain water
and the like, and a static charge is inhibited from being generated
on a surface thereof, so that dirts and dusts in the air are less
liable to be adsorbed thereon. Further, the sheet 4 of the present
invention is used, and therefore the alkyl silicate is less liable
to drop out due to a three-dimensional cross-linking structure
thereof, so that the sheet is improved in a scratch resistance and
liable to keep a hydrophilicity and an antifog property over a long
period of time.
[0235] The coating composition 4 used for forming the sheet 4 of
the present invention can be used in the form of a sheet without
providing thereon the other layers described above by curing a
coating film of the above coating composition 4. To be specific,
the coating composition 4 can be used in the form of a sheet, for
example, by forming a film-like coating film by a publicly known
coating method such as gravure coating, roll coating and the like
and then curing the coating film. The above coating film may be
formed directly on a structure targeted for coating or may be
formed by laminating on a peelable transfer sheet substrate. The
coating film can be cured, for example, by irradiating with an
ionizing radiation. A method of curing by irradiating with an
ionizing radiation is the same method as, for example, a method of
curing in forming the surface protective layer of the sheet 1.
[0236] A thickness of the sheet obtained by curing a coating film
of the coating composition 4 shall not specifically be restricted
and can suitably be set according to the characteristics of the
finished product, and it is usually 0.1 to 50 .mu.m, preferably 1
to 20 .mu.m. The above sheet has the same performances as those of
the surface protective layer formed by using the coating
composition 4 described above.
Sheet 5:
[0237] A fifth embodiment of the sheet of the present invention
(hereinafter referred to merely as the "sheet 5") has a surface
protective layer obtained by cross-liking and curing a coating
composition 5, and it shall not specifically be restricted as long
as it has the above surface protective layer. A preferred
embodiment of the sheet 5 is the same as the embodiment shown in
FIG. 4, that is, that of the sheet 3 described above.
EXAMPLES
[0238] Next, the present invention shall be explained in further
details with reference to examples, but the present invention shall
by no means be restricted by these examples.
1. Coating Composition 1 and Sheet 1
Evaluation Methods:
(1-1) Evaluation of Weatherability (Weatherability Test):
[0239] The sheets obtained in the examples and the comparative
examples were set in Metal Weather manufactured by DAIPLA WINTES
Co., Ltd. and subjected to a weatherability test in which they were
left standing on light conditions (illuminance: 60 mW/cm.sup.2,
black panel temperature: 63.degree. C., humidity in the layer: 50%
RH) for 20 hours, on dew condensation conditions (illuminance: 0
mW/cm.sup.2, black panel temperature: 30.degree. C., humidity in
the layer: 98% RH) for 4 hours and on a water spraying condition
(10 seconds before and after the dew condensation conditions) for
800 hours. After the above test, the sheets were held for 2 days on
the conditions of 25.degree. C. and 50% RH, and then an appearance
of cracks and whitening on a surface of the sheet was evaluated
according to the following criteria: [0240] .circleincircle.:
appearance change was not observed at all [0241] .largecircle.:
appearance change was scarcely observed [0242] .DELTA.: appearance
change was slightly observed, but problems were not involved
practically [0243] X: appearance change was notably observed
(1-2) Evaluation of Weatherability Adhesive Property:
[0244] The sheet subjected to the weatherability test described
above was subjected once to operation in which Cellotape
(registered trade name) manufactured by Nichiban Co., Ltd. was
stuck on a surface thereof and rapidly peeled off. Then, whether or
not the respective layers provided on the base material were peeled
off was confirmed by visual observation and evaluated according to
the following criteria: [0245] .largecircle.: layers were not
peeled off at all [0246] .DELTA.: layers were slightly peeled off,
but problems were not involved practically [0247] X: layers were
notably peeled off
(1-3) Evaluation of Stickiness (Bleed Out):
[0248] The sheets obtained in the examples and the comparative
examples were stored for 24 hours on the condition of 80.degree.
C., and then a surface of the decorated sheet was touched with a
finger and evaluated according to the following criteria: [0249]
.largecircle.: stickiness was not observed at all [0250] .DELTA.:
stickiness brought about by bleeding of the UV absorber and the
like was slightly observed, but problems were not involved
practically [0251] X: stickiness brought about by bleeding was
notably observed
(1-4) Evaluation of Solvent Resistance:
[0252] A gauze was set to a plummet of 300 g/cm.sup.2 by a rubber
band and impregnated with ethyl acetate. The plummet was
reciprocated 50 times in a lateral direction on the surfaces of the
sheets obtained in the respective examples and comparative
examples, and the surfaces of the sheets were visually observed and
evaluated according to the following criteria: [0253]
.largecircle.: change on the surface of the sheet was not observed
at all [0254] .DELTA.: change on the surface of the sheet was
slightly observed, but problems were not involved practically
[0255] X: change on the surface of the sheet was notably
observed
(1-5) Evaluation of Yellowing:
[0256] In the respective examples and comparative examples, a color
on a surface of the sheet immediately after irradiated with an
electron beam was evaluated according to the following criteria:
[0257] .largecircle.: yellowing was not observed at all [0258]
.DELTA.: yellowing was slightly observed, but problems were not
involved practically [0259] X: yellowing was notably observed
(1-6) Evaluation of Scratch Resistance:
[0260] The sheets obtained in the respective examples and
comparative examples were rubbed thereon in five reciprocations by
using a steel wool on which a weight of 300 g/cm.sup.2 was applied,
and the appearances thereof were visually evaluated. They were
evaluated according to the following criteria: [0261]
.largecircle.: change was scarcely observed on the appearance
[0262] .DELTA.: slight scratches and gloss change were observed on
the appearance [0263] X: scratches and gloss change were observed
on the appearance
(1-7) Evaluation of Transparency:
[0264] The states on the surfaces of the sheets obtained in the
respective examples and comparative examples were evaluated
according to the following criteria: [0265] .largecircle.: haze
feeling (cloudy feeling) was not observed at all [0266] .DELTA.:
haze feeling was slightly observed, but problems were not involved
practically [0267] X: haze feeling was observed
(1-8) Evaluation of Self-Cleaning Property (Initial Performance)
and Persistence Thereof:
[0268] The sheets obtained in the examples and the comparative
examples were set outdoors toward the south at a gradient of
45.degree.. Then, an adhesion and deposition state of contaminants
on the surface was evaluated according to the following criteria to
set it to evaluation of the initial performance. Further, the
sheets obtained in the examples and the comparative examples were
subjected to an outdoor exposure test in which they were set
outdoors toward the south at a gradient of 45.degree. and then left
standing for 3 months. Then, an adhesion and deposition state of
contaminants on the surface was evaluated according to the
following criteria to set it to evaluation of a persistence
thereof: [0269] .circleincircle.: adhesion and deposition of
contaminants were not observed at all [0270] .largecircle.:
adhesion and deposition of contaminants were scarcely observed
[0271] .DELTA.: adhesion and deposition of contaminants were
slightly observed, but problems were not involved practically
[0272] X: adhesion and deposition of contaminants were notably
observed
Example 1-1
[0273] A resin sheet comprising a transparent polypropylene resin
(thickness: 80 .mu.m) was prepared as the base material 2. A
surface and a rear face thereof were subjected to corona discharge
treatment, and then a composition for forming a primer layer having
the following composition was coated (2.5 g/m.sup.2) on the above
surface to form a primer layer (thickness: 2 .mu.m). Next, an
ionizing radiation-curable resin composition having the following
composition was prepared to form a coating film by a gravure
coating method, and the coating film described above was
cross-linked and cured by irradiating with an electron beam on the
conditions of 175 keV and 5 Mrad (50 kGy), whereby a surface
protective layer (5 g/m.sup.2) was formed to obtain a sheet. A
thickness of the surface protective layer was 5 .mu.m.
[0274] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 1.
Composition of Composition for Forming a Primer Layer:
[0275] It is a composition obtained by mixing a resin composition
and a curing agent each shown below in a proportion of 100:5 (mass
ratio).
Resin Composition:
TABLE-US-00001 [0276] Polycarbonate base urethane acrylate (mass
ratio 100 parts by mass of a urethane component and an acryl
component in the polycarbonate base urethane acrylate: 70/30)
Hydroxyphenyltriazine base UV absorber 15 parts by mass (Tinuvin
400 (trade name), manufactured by Ciba Specialty Chemicals K.K.)
Hydroxyphenyltriazine base UV absorber 5 parts by mass (Tinuvin 479
(trade name), manufactured by Ciba Specialty Chemicals K.K.)
Hindered amine base light stabilizer 6 parts by mass (Tinuvin 123
(trade name), manufactured by Ciba Specialty Chemicals K.K.)
Curing Agent:
[0277] Hexamethylenediisocyanate
Composition of Ionizing Radiation-Curable Resin Composition:
TABLE-US-00002 [0278] Caprolactone base urethane acrylate oligomer
100 parts by mass (trifunctional, (weight average molecular weight:
about 1200) Triazine base UV absorber (Tinuvin 479 (trade name), 2
parts by mass 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,
6-bis(4-phenylphenyl)-1,3,5-triazine, manufactured by Ciba
Specialty Chemicals K.K.) Light stabilizer having a reactive
functional group 6 parts by mass (trade name: Sanol LS-3410,
1,2,2,6, 6-pentamethyl-4-piperidinylmethacrylate, manufactured by
Ciba Specialty Chemicals K.K.)
Example 1-2
[0279] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, a content of the triazine base UV
absorber contained in the ionizing radiation-curable resin
composition was changed to 6 parts by mass.
[0280] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 1.
Example 1-3
[0281] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, 10 parts by mass of a silicate compound
having a vinyl group at an end represented by the following
Chemical Formula (4) was further added to the ionizing
radiation-curable resin composition.
[0282] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 1.
##STR00004##
Example 1-4
[0283] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, a mixed resin of polycarbonate base
urethane acrylate and acryl polyol (mass ratio of a urethane
component and an acryl component in the polycarbonate base urethane
acrylate: 70/30, a mass ratio of urethane acrylate and acryl
polyol: 50/50) was used in place of the polycarbonate base urethane
acrylate in the primer layer.
[0284] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 1.
Example 1-5
[0285] A resin sheet comprising a colored polypropylene resin
(thickness: 80 .mu.m) was prepared as the base material 2. A
surface and a rear face thereof were subjected to corona discharge
treatment, and then a wood grain pattern was formed on a surface
thereof by gravure printing to obtain a pattern-printed layer 3. On
the other hand, a rear face primer layer 7 (thickness: 2 .mu.m)
comprising a urethane base resin as a binder was formed on a rear
face thereof by gravure printing.
[0286] A transparent resin layer 4 (thickness: 80 .mu.m) obtained
by melting a polypropylene base thermoplastic resin by a T die was
formed, and the transparent resin layer 4 was laminated thereon by
a dry lamination method. A surface of the transparent resin layer 4
was heated by means of a heater of an infrared non-contact system
to soften a surface of the transparent resin layer 4, and a surface
of the transparent resin layer 4 at a side opposite to the base
material 2 was subjected immediately to emboss processing by hot
pressing to provide an irregular pattern of a wood grain conduit
groove pattern.
[0287] Next, a surface of the transparent resin layer 4 was
subjected to corona discharge treatment, and then it was subjected
to wiping processing. An ink composition used for the wiping
processing was prepared by adding 5 by mass of a colorant
(containing carbon black, isoindolinone and quinacridone) and 15%
by mass of silica particles (non-treated silica "commercially
available product", average particle diameter: 3 .mu.m) to the
composition for forming a primer layer used in Example 1-1.
[0288] The above ink composition was coated on the transparent
resin layer 4 described above, and a coated face thereof was
subjected to wiping processing, whereby a colored resin layer 9 was
formed in the concave parts of the transparent resin layer 4. A
coating amount thereof was 1.5 g/m.sup.2. Next, the ink composition
used for forming the colored resin layer 9 described above was
coated thereon to form a primer layer 5 (2.5 g/m.sup.2).
[0289] Next, a composition was prepared by adding to the ionizing
radiation-curable resin composition used in Example 1-1, 10 parts
by mass of silica (oil absorption: 200 to 300 ml/100 g, apparent
specific gravity: 0.08 to 0.16 g/cm.sup.3) having an average
particle diameter of 5 .mu.m, 5 parts by mass of silica (oil
absorption: 0 to 50 ml/100 g, apparent specific gravity: 0.45 to
0.85 g/cm.sup.3) having an average particle diameter of 4 .mu.m and
5 parts by mass of wax (aliphatic wax, melting point: 110 to
200.degree. C.) each based on 100 parts by mass of the caprolactone
base urethane acrylate contained in the above composition, and it
was used to form a coating film by gravure coating. Then, the
coating film described above was cross-linked and cured by
irradiating with an electron beam on the conditions of 175 keV and
5 Mrad (50 kGy), whereby a surface protective layer (5 g/m.sup.2)
was formed to obtain a sheet. A thickness of the surface protective
layer was 5 .mu.m.
Example 1-6
[0290] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, acrylpolyol was used alone as the resin
for forming the primer layer. The sheet thus obtained was evaluated
for the items described above, and the evaluation results thereof
are shown in Table 1.
Example 1-7
[0291] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, polyester base urethane acrylate was
used as the resin for forming the primer layer. The sheet thus
obtained was evaluated for the items described above, and the
evaluation results thereof are shown in Table 1.
Example 1-8
[0292] A sheet was prepared in the same manner as in Example 1-3,
except that in Example 1-3, the silicate compound was changed to
alkyl silicate 1-1 (MS-56 (trade name), manufactured by Mitsubishi
Chemical Corporation, an average decamer (mixture of a decamer to a
dodecamer) of alkyl silicate in which all of R.sup.12 to R.sup.15
in Formula (3) described above are methyl, weight average molecular
weight: 1100 to 1300). The sheet thus obtained was evaluated for
the items described above, and the evaluation results thereof are
shown in Table 1.
Example 1-9
[0293] A sheet was prepared in the same manner as in Example 1-3,
except that in Example 1-3, the silicate compound was changed to
alkyl silicate 1-2 (MS-56S (trade name), manufactured by Mitsubishi
Chemical Corporation, an average hexadecamer (mixture of a
tetradecamer to an octadodecamer) of alkyl silicate in which all of
R.sup.12 to R.sup.15 in Formula (3) described above are methyl,
weight average molecular weight: 1500 to 1900). The sheet thus
obtained was evaluated for the items described above, and the
evaluation results thereof are shown in Table 1.
Example 1-10
[0294] A sheet was prepared in the same manner as in Example 1-3,
except that in Example 1-3, the silicate compound was changed to
alkyl silicate 1-3 (Methyl Silicate 51 (trade name), manufactured
by COLCOAT CO., Ltd., an average heptamer of alkyl silicate in
which all of R.sup.12 to R.sup.15 in Formula (3) described above
are methyl, weight average molecular weight: 789). The sheet thus
obtained was evaluated for the items described above, and the
evaluation results thereof are shown in Table 1.
Example 1-11
[0295] A sheet was prepared in the same manner as in Example 1-3,
except that in Example 1-3, the silicate compound was changed to
alkyl silicate 1-4 having methoxy and ethoxy (EMS-485 (trade name),
manufactured by COLCOAT CO., Ltd., an average decamer of alkyl
silicate in which R.sup.12 and R.sup.13 in Formula (3) described
above are methyl and in which R.sup.14 and R.sup.15 are ethyl,
molecular weight: 1300). The sheet thus obtained was evaluated for
the items described above, and the evaluation results thereof are
shown in Table 1.
Comparative Example 1-1
[0296] The same materials and production process as in Example 1-1
were used to prepare a sheet, except that in Example 1-1, a
polyether base urethane acrylate oligomer (difunctional, molecular
weight: about 3000) was used in place of the caprolactone base
urethane acrylate contained in the ionizing radiation-curable resin
composition, and the evaluation results thereof are shown in Table
2.
Comparative Example 1-2
[0297] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, 2% by mass of a benzotriazole base UV
absorber (Tinuvin 384-2 (trade name), manufactured by Ciba
Specialty Chemicals K.K.) was added in place of the triazine base
UV absorber contained in the ionizing radiation-curable resin
composition, and the evaluation results thereof are shown in Table
2.
Comparative Example 1-3
[0298] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, 6% by mass of a hindered amine base
light stabilizer (Tinuvin 123 (trade name), manufactured by Ciba
Specialty Chemicals K.K.) having no reactive functional group was
added in place of the light stabilizer having a reactive functional
group contained in the ionizing radiation-curable resin
composition, and the evaluation results thereof are shown in Table
2.
Comparative Example 1-4
[0299] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, 6% by mass of the triazine base UV
absorber contained in the ionizing radiation-curable resin
composition was added and that 6% by mass of the hindered amine
base light stabilizer (Tinuvin 123 (trade name), manufactured by
Ciba Specialty Chemicals K.K.) having no reactive functional group
was added in place of the light stabilizer having a reactive
functional group contained in the ionizing radiation-curable resin
composition. The evaluation results thereof are shown in Table
2.
Comparative Example 1-5
[0300] A sheet was prepared in the same manner as in Example 1-1,
except that in Example 1-1, 6% by mass of a powdery hindered amine
base light stabilizer (Tinuvin 144 (trade name), manufactured by
Ciba Specialty Chemicals K.K.) was added in place of the light
stabilizer having a reactive functional group contained in the
ionizing radiation-curable resin composition. The evaluation
results thereof are shown in Table 2.
TABLE-US-00003 TABLE 1 Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9
1-10 1-11 Base Transparent polypropylene .largecircle.
.largecircle. .largecircle. .largecircle. -- .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. material resin Colored polypropylene -- -- -- --
.largecircle. -- -- -- -- -- -- resin Primer Resin Polycarbonate
100 100 100 -- 100 -- -- 100 100 100 100 layer base urethane
acrylate Mixed resin -- -- -- 100 -- -- -- -- -- -- -- Acrylpolyol
-- -- -- -- -- 100 -- -- -- -- -- Polyester base -- -- -- -- -- --
100 -- -- -- -- urethane acrylate UV Hydroxyphenyl- 20 20 20 20 20
20 20 20 20 20 20 absorber triazine base Light Hindered amine 6 6 6
6 6 6 6 6 6 6 6 stabilizer base Coating Resin Caprolactone 100 100
100 100 100 100 100 100 100 100 100 agent base Polyether base -- --
-- -- -- -- -- -- -- -- -- UV Triazine base 2 6 2 2 2 2 2 2 2 2 2
absorber Benzotriazole -- -- -- -- -- -- -- -- -- -- -- base Light
Reactive 6 6 6 6 6 6 6 6 6 6 6 stabilizer functional group present
No reactive -- -- -- -- -- -- -- -- -- -- -- functional group
(liquid) No reactive -- -- -- -- -- -- -- -- -- -- -- functional
group (powder) Silicate compound having -- -- 10 -- -- -- -- -- --
-- -- reactive functional group Alkyl silicate 1-1 -- -- -- -- --
-- -- 10 -- -- -- Alkyl silicate 1-2 -- -- -- -- -- -- -- -- 10 --
-- Alkyl silicate 1-3 -- -- -- -- -- -- -- -- -- 10 -- Alkyl
silicate 1-4 -- -- -- -- -- -- -- -- -- -- 10 Evaluation
Weatherability .circleincircle. .circleincircle. .circleincircle.
.largecircle.~.circleincircle. .circleincircle. .largecircle.
.DELTA. .largecircle. .largecircle. .largecircle. .largecircle.
Weatherability adhesive .circleincircle. .circleincircle.
.circleincircle. .largecircle.~.circleincircle. .circleincircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. property Stickiness .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Solvent resistance .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. .DELTA.
.largecircle. Yellowing .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. Scratch
resistance .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Transparency
.largecircle. .largecircle. .largecircle. .largecircle. --
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Self-cleaning property -- --
.largecircle. -- -- -- -- .circleincircle. .circleincircle.
.largecircle. .largecircle. (initial) Persistence of self- -- --
.circleincircle. -- -- -- -- .largecircle. .largecircle.
.largecircle. .largecircle. cleaning property Remark: all the
values of the primer layer and the coating agents in the table show
parts by mass.
TABLE-US-00004 TABLE 2 Comparative Example 1-1 1-2 1-3 1-4 1-5 Base
Transparent polypropylene .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. material resin Colored polypropylene --
-- -- -- -- resin Primer Resin Polycarbonate 100 100 100 100 100
layer base urethane acrylate Mixed resin -- -- -- -- -- Acrylpolyol
-- -- -- -- -- Polyester base -- -- -- -- -- urethane acrylate UV
Hydroxyphenyl- 20 20 20 20 20 absorber triazine base Light Hindered
amine 6 6 6 6 6 stabilizer base Coating Resin Caprolactone -- 100
100 100 100 agent base Polyether base 100 -- -- -- -- UV Triazine
base 2 -- 2 6 2 absorber Benzotriazole -- 2 -- -- -- base Light
Reactive 6 6 -- -- -- stabilizer functional group present No
reactive -- -- 6 6 -- functional group (liquid) No reactive -- --
-- -- 6 functional group (powder) Silicate compound having -- -- --
-- -- reactive functional group Alkyl silicate 1-1 -- -- -- -- --
Alkyl silicate 1-2 -- -- -- -- -- Alkyl silicate 1-3 -- -- -- -- --
Alkyl silicate 1-4 -- -- -- -- -- Evaluation Weatherability .DELTA.
.largecircle. X .largecircle. X Weatherability adhesive X
.largecircle. .DELTA. .largecircle. .DELTA. property Stickiness
.largecircle. .largecircle. .DELTA. X .largecircle. Solvent
resistance .largecircle. .largecircle. .DELTA. X .DELTA. Yellowing
.largecircle. X .largecircle. .largecircle. .largecircle. Scratch
resistance .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Transparency .largecircle. .largecircle.
.largecircle. .largecircle. .DELTA. Self-cleaning property -- -- --
-- -- (initial) Persistence of self- -- -- -- -- -- cleaning
property Remark: all the values of the primer layer and the coating
agents in the table show parts by mass.
2. Coating Composition 2 and Sheet 2
Evaluation Methods:
(2-1) Evaluation of Self-Cleaning Property:
[0301] The sheets obtained in the examples and the comparative
examples were subjected to an outdoor exposure test in which they
were set outdoors toward the south at a gradient of 45.degree. and
left standing for 3 months. Then, an adhesion and deposition state
of contaminants on the surface was evaluated according to the
following criteria: [0302] .largecircle.: adhesion and deposition
of contaminants were scarcely observed [0303] .DELTA.: adhesion and
deposition of contaminants were slightly observed, but problems
were not involved practically [0304] X: adhesion and deposition of
contaminants were notably observed
(2-2) Evaluation of Persistence of Self-Cleaning Property:
[0305] The sheets obtained in the examples and the comparative
examples were coated with a salad oil colored by a red dye and then
washed with water. Thereafter, an adhesion and deposition state of
contaminants on the surface was evaluated according to the
following criteria: [0306] .circleincircle.: change was not
observed at all [0307] .largecircle.: adhesion and deposition of
contaminants were scarcely observed [0308] .DELTA.: adhesion and
deposition of contaminants were slightly observed, but problems
were not involved practically [0309] X: adhesion and deposition of
contaminants were notably observed
(2-3) Warm Water Whitening Resistance:
[0310] The sheets obtained in the examples and the comparative
examples were dipped in warm water of 50.degree. C. and kept for 2
days, and then a whitening state on the sheet surface was evaluated
according to the following criteria: [0311] .largecircle.:
appearance change was not observed at all [0312] .DELTA.:
appearance change was slightly observed, but problems were not
involved practically [0313] X: appearance change was notably
observed
(2-4) Measurement of Surface Resistance:
[0314] The surface resistances of the sheets obtained in the
examples and the comparative examples were measured by means of a
digital insulation meter (manufactured by TOA-DKK CORPORATION).
(2-5) Charge Decay Rate Half-Time:
[0315] The charge decay rate half-times of the sheets obtained in
the examples and the comparative examples were measured by means of
an honest meter (manufactured by Shindo Electrostatic Co.,
Ltd.).
(2-6) Evaluation of Weatherability (Weatherability Test):
[0316] The sheets obtained in the examples and the comparative
examples were set in Metal Weather manufactured by DAIPLA WINTES
Co., Ltd. and subjected to a weatherability test in which they were
left standing on light conditions (illuminance: 60 mW/cm.sup.2,
black panel temperature: 63.degree. C., humidity in the layer: 50%
RH) for 20 hours, on dew condensation conditions (illuminance: 0
mW/cm.sup.2, black panel temperature: 30.degree. C., humidity in
the layer: 98% RH) for 4 hours and on a water spraying condition
(10 seconds before and after the dew condensation conditions) for
800 hours. After the above test, the sheets were held for 2 days on
the conditions of 25.degree. C. and 50% RH, and then an appearance
change of cracks and whitening on a surface of the sheet was
evaluated according to the following criteria: [0317]
.circleincircle.: appearance change was not observed at all [0318]
.largecircle.: appearance change was scarcely observed [0319]
.DELTA.: appearance change was slightly observed, but problems were
not involved practically [0320] X: appearance change was notably
observed
(2-7) Evaluation of Weatherability Adhesive Property:
[0321] The sheet subjected to the weatherability test described
above was subjected once to operation in which Cellotape
(registered trade name) manufactured by Nichiban Co., Ltd. was
stuck on a surface thereof and rapidly peeled off. Then, whether or
not the respective layers provided on the base material were peeled
off was confirmed by visual observation and evaluated according to
the following criteria: [0322] .largecircle.: layers were not
peeled off at all [0323] .DELTA.: layers were slightly peeled off,
but problems were not involved practically [0324] X: layers were
notably peeled off
(2-8) Evaluation of Stickiness (Bleed Out):
[0325] The sheets obtained in the examples and the comparative
examples were stored for 24 hours on the condition of 80.degree.
C., and then a surface of the decorated sheet was touched with a
finger and evaluated according to the following criteria: [0326]
.largecircle.: stickiness was not observed at all [0327] .DELTA.:
stickiness brought about by bleeding of the UV absorber and the
like was slightly observed, but problems were not involved
practically [0328] X: stickiness brought about by bleeding was
notably observed
(2-9) Evaluation of Solvent Resistance:
[0329] A gauze was set to a plummet of 300 g/cm.sup.2 by a rubber
band and impregnated with ethyl acetate. The plummet was
reciprocated 50 times in a lateral direction on the surfaces of the
sheets obtained in the respective examples and comparative
examples, and the surfaces of the sheets were visually observed and
evaluated according to the following criteria: [0330]
.largecircle.: change on the surface of the sheet was not observed
at all [0331] .DELTA.: change on the surface of the sheet was
slightly observed, but problems were not involved practically
[0332] X: change on the surface of the sheet was notably
observed
(2-10) Evaluation of Yellowing:
[0333] In the respective examples and comparative examples, a color
on a surface of the sheet immediately after irradiated with an
electron beam was evaluated according to the following criteria:
[0334] .largecircle.: yellowing was not observed at all [0335]
.DELTA.: yellowing was slightly observed, but problems were not
involved practically [0336] X: yellowing was notably observed
(2-11) Evaluation of Scratch Resistance:
[0337] The sheets obtained in the respective examples and
comparative examples were rubbed thereon in five reciprocations by
using a steel wool on which a weight of 300 g/cm.sup.2 was applied,
and the surfaces thereof were visually evaluated. They were
evaluated according to the following criteria: [0338]
.largecircle.: change was scarcely observed on the appearance
[0339] .DELTA.: slight scratches and gloss change were observed on
the appearance [0340] X: scratches were observed on the appearance,
and gloss change was observed
(2-12) Evaluation of Transparency:
[0341] The states on the surfaces of the sheets obtained in the
respective examples and comparative examples were evaluated
according to the following criteria: [0342] .largecircle.: haze
feeling (cloudy feeling) was not observed at all [0343] .DELTA.:
haze feeling was slightly observed, but problems were not involved
practically [0344] X: haze feeling was observed
Example 2-1
[0345] A resin sheet comprising a transparent polypropylene resin
(thickness: 80 .mu.m) was prepared as the base material 2. A
surface and a rear face thereof were subjected to corona discharge
treatment, and then a composition for forming a primer layer having
the following composition was coated (2.5 g/m.sup.2) on the above
surface to form a primer layer (thickness: 2 .mu.m). Next, an
ionizing radiation-curable resin composition containing a silicate
compound having a reactive functional group which had the following
composition was prepared to form a coating film by a gravure
coating method, and the coating film described above was
cross-linked and cured by irradiating with an electron beam on the
conditions of 175 keV and 5 Mrad (50 kGy), whereby a surface
protective layer (5 g/m.sup.2) was formed to obtain a sheet. A
thickness of the surface protective layer was 5 .mu.m.
[0346] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 3.
Composition of Composition for Forming a Primer Layer:
[0347] It is a composition obtained by mixing a resin composition
and a curing agent each shown below in a proportion of 100:5 (mass
ratio).
Resin Composition:
TABLE-US-00005 [0348] Polycarbonate base urethane acrylate and
acrylpolyol 100 parts by mass (mass ratio of a urethane component
and an acryl component in the polycarbonate base urethane acrylate:
70/30, a mass ratio of urethane acrylate and acrylpolyol: 50/50)
Hydroxyphenyltriazine base UV absorber 15 parts by mass (Tinuvin
400 (trade name), manufactured by Ciba Specialty Chemicals K.K.)
Hydroxyphenyltriazine base UV absorber 4 parts by mass (Tinuvin 479
(trade name), manufactured by Ciba Specialty Chemicals K.K.)
Hindered amine base light stabilizer (Tinuvin 123 3 parts by mass
(trade name), manufactured by Ciba Specialty Chemicals K.K.)
Curing Agent:
[0349] Hexamethylenediisocyanate
Composition of Ionizing Radiation-Curable Resin Composition:
TABLE-US-00006 [0350] Polyether base urethane acrylate oligomer 100
parts by mass (trifunctional, molecular weight: 2000) Silicate
compound represented by Chemical Formula 10 parts by mass (4)
described above which has a vinyl group at an end Triazine base UV
absorber (Tinuvin 479 (trade name), 2 parts by mass
2-(2-hydroxy-4-[1-octyloxycarbonylethoxy] phenyl)-4,
6-bis(4-phenylphenyl)-1,3,5-triazine, manufactured by Ciba
Specialty Chemicals K.K.) Light stabilizer having a reactive
functional group 6 parts by mass (trade name: Sanol LS-3410,
1,2,2,6,6-pentamethyl- 4-piperidinylmethacrylate, manufactured by
Ciba Specialty Chemicals K.K.)
Example 2-2
[0351] A sheet was prepared in the same manner as in Example 2-1,
except that in Example 2-1, the ionizing radiation-curable resin
composition was changed to caprolactone base urethane acrylate
(trifunctional, weight average molecular weight: about 1200) and
that the addition amounts of the UV absorber and the light
stabilizer were changed to 2 parts by mass and 6 parts by mass
respectively.
[0352] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 3.
Example 2-3
[0353] A sheet was prepared in the same manner as in Example 2-2,
except that in Example 2-2, the base material was changed to a
transparent polypropylene resin (thickness: 80 .mu.m, an antistatic
agent content: 12.5% by mass) containing a high polymer type
antistatic agent (Pelestat 300 (trade name), polyether/polyolefin
block copolymer, manufactured by Sanyo Chemical Industries,
Ltd.).
[0354] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 3.
Example 2-4
[0355] A resin sheet comprising a colored polypropylene resin
(thickness: 80 .mu.m) was prepared as the base material 2. A
surface and a rear face thereof were subjected to corona discharge
treatment, and then a wood grain pattern was formed on a surface
thereof by gravure printing to obtain a pattern-printed layer 3. On
the other hand, a rear face primer layer 7 (thickness: 2 .mu.m)
comprising a urethane base resin as a binder was formed on a rear
face thereof by gravure printing.
[0356] Then, a transparent resin layer 4 (thickness: 80 .mu.m)
obtained by melting a polypropylene base thermoplastic resin by a T
die was formed, and the transparent resin layer 4 was laminated by
a dry lamination method on an adhesive layer 8 (thickness in a dry
state: 15 .mu.m) prepared by coating a coating liquid comprising a
two-component curing type urethane resin.
[0357] Next, a surface of the transparent resin layer 4 was heated
by means of a heater of an infrared non-contact system to soften a
surface of the transparent resin layer 4. Then, a surface of the
transparent resin layer 4 at a side opposite to the base material 2
was subjected immediately to emboss processing by hot pressing to
provide an irregular pattern of a wood grain conduit groove
pattern.
[0358] Next, a surface of the transparent resin layer 4 was
subjected to corona discharge treatment, and then it was subjected
to wiping processing. An ink composition used for the wiping
processing was prepared by adding 5% by mass of a colorant
(containing carbon black, isoindolinone and quinacridone) and 15%
by mass of silica particles (non-treated silica "commercially
available product", average particle diameter: 3 .mu.m) to the
composition for forming a primer layer used in Example 1-1.
[0359] The above ink composition was coated on the transparent
resin layer 4 described above, and a coated face thereof was
subjected to wiping processing, whereby a colored resin layer 9 was
formed in the concave parts of the transparent resin layer 4. A
coating amount thereof was 1.5 g/m.sup.2. Next, the ink composition
used for forming the colored resin layer 9 described above was
coated thereon to form a primer layer 5 (2.5 g/m.sup.2).
[0360] Next, a composition was prepared by adding to the ionizing
radiation-curable resin composition used in Example 2-2, 10 parts
by mass of silica (oil absorption: 200 to 300 ml/100 g, apparent
specific gravity: 0.08 to 0.16 g/cm.sup.3) having an average
particle diameter of 5 .mu.m, 5 parts by mass of silica (oil
absorption: 0 to 50 ml/100 g, apparent specific gravity: 0.45 to
0.85 g/cm.sup.3) having an average particle diameter of 4 .mu.m and
5 parts by mass of wax (aliphatic wax, melting point: 110 to
200.degree. C.) each based on 100 parts by mass of the caprolactone
base urethane acrylate contained in the above resin composition,
and it was used to form a coating film by gravure coating. Then,
the coating film described above was cross-linked and cured by
irradiating with an electron beam on the conditions of 175 keV and
5 Mrad (50 kGy), whereby a surface protective layer (5 g/m.sup.2)
was formed to obtain a sheet. A thickness of the surface protective
layer was 5 .mu.m.
Comparative Example 2-1
[0361] A sheet was prepared in the same manner as in Example 2-2,
except that in Example 2-2, the silicate compound contained in the
ionizing radiation-curable resin composition was changed to ethyl
silicate (Ethyl Silicate 28 (trade name), a monomer, manufactured
by COLCOAT CO., Ltd.).
Comparative Example 2-2
[0362] A sheet was prepared in the same manner as in Example 2-2,
except that in Example 2-2, the silicate compound contained in the
ionizing radiation-curable resin composition was changed to ethyl
silicate (Ethyl Silicate 48 (trade name), a decamer, manufactured
by COLCOAT CO., Ltd.).
Comparative Example 2-3
[0363] A sheet was prepared in the same manner as in Example 2-2,
except that in Example 2-2, the silicate compound contained in the
ionizing radiation-curable resin composition was removed.
TABLE-US-00007 TABLE 3 Example Comparative Example 2-1 2-2 2-3 2-4
2-1 2-2 2-3 Base Transparent polypropylene .largecircle.
.largecircle. -- -- .largecircle. .largecircle. .largecircle.
material resin (no antistatic agent) Transparent polypropylene --
-- .largecircle. -- -- -- -- resin (antistatic agent contained)
Colored polypropylene resin -- -- -- .largecircle. -- -- -- Coating
Resin Polyether base 100 -- -- -- -- -- -- agent Caprolactone --
100 100 100 100 100 100 base Silicate Reactive 10 10 10 10 -- -- --
compound functional group present Ethyl silicate -- -- -- -- 10 --
-- (monomer) Ethyl silicate -- -- -- -- -- 10 -- (decamer) UV
absorber Triazine base 2 2 2 2 2 2 2 Light Hindered amine 6 6 6 6 6
6 6 stabilizer base Evaluation Self-cleaning property .largecircle.
.largecircle. .circleincircle. .largecircle. X .largecircle. X
Persistence of self-cleaning .largecircle. .circleincircle.
.circleincircle. .largecircle. X .DELTA. X property Warm water
whitening .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .DELTA. .largecircle. resistance Surface resistivity
(.OMEGA./.quadrature.) 10.sup.14 10.sup.14 10.sup.10 10.sup.14
10.sup.14 10.sup.14 10.sup.14 Charge decay rate half-time 3 .times.
10.sup.4 3 .times. 10.sup.4 3 to 3 .times. 10.sup.4 3 .times.
10.sup.4 3 .times. 10.sup.4 3 .times. 10.sup.4 (second) or more or
more 5 .times. 10.sup.4 or more or more or more or more
Weatherability .DELTA. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Weatherability adhesive
.DELTA. .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. property Stickiness .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. .DELTA.
.largecircle. Solvent resistance .largecircle. .largecircle.
.largecircle. .largecircle. .DELTA. .DELTA. .largecircle. Yellowing
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Scratch resistance
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. Transparency
.largecircle. .largecircle. .largecircle. -- .largecircle. .DELTA.
.largecircle. Remark: all the values of the coating agents show
parts by mass.
3. Coating Composition 3 and Sheet 3
Evaluation Methods:
(3-1) Evaluation of Self-Cleaning Property (Initial Performance)
and Persistence Thereof:
[0364] The films obtained in the examples and the comparative
examples were set outdoors toward the south at a gradient of
45.degree.. Then, an adhesion and deposition state of contaminants
on the surface was evaluated according to the following criteria to
set it to evaluations of the initial performances. Also, the films
obtained in the examples and the examples were subjected to an
outdoor exposure test in which they were set outdoors toward the
south at a gradient of 45.degree. and then left standing for 3
months. Then, an adhesion and deposition state of contaminants on
the surface was evaluated according to the following criteria to
set it to evaluations of a persistence thereof: [0365]
.circleincircle.: adhesion and deposition of contaminants were not
observed at all [0366] .largecircle.: adhesion and deposition of
contaminants were scarcely observed [0367] .DELTA.: adhesion and
deposition of contaminants were slightly observed, but problems
were not involved practically [0368] X: adhesion and deposition of
contaminants were notably observed
(3-2) Evaluation of Visible Light Transmission Property (Initial
Performance) and Persistence Thereof:
[0369] the visible light transmission factors of the films obtained
in the examples and the comparative examples were measured
according to JIS K7361-1 (test method for a whole transmission
factor of a plastic-transparent material), and they were evaluated
as a visible light transmission factor (initial performance)
according to the following criteria. Further, the sheets obtained
in the examples and the comparative examples were subjected to an
outdoor exposure test in which they were set outdoors toward the
south at a gradient of 45.degree. and then left standing for 3
months. Then, the sheets were evaluated in the same manner as
described above to set it to evaluation of a persistence of the
visible light transmission factor. [0370] .circleincircle.: visible
light transmission factor is 80% or more [0371] .largecircle.:
visible light transmission factor is 70% or more and less than 80%
[0372] .DELTA.: visible light transmission factor is 50% or more
and less than 70% [0373] X: visible light transmission factor is
less than 50%
(3-3) UV Ray Blocking Persistence:
[0374] The films obtained in the examples and the comparative
examples were set in Metal Weather manufactured by DAIPLA WINTES
Co., Ltd. and subjected to a weatherability test in which they were
left standing on light conditions (illuminance: 60 mW/cm.sup.2,
black panel temperature: 63.degree. C., humidity in the layer: 50%
RH) for 20 hours, on dew condensation conditions (illuminance: 0
mW/cm.sup.2, black panel temperature: 30.degree. C., humidity in
the layer: 98% RH) for 4 hours and then on a water spraying
condition (10 seconds before and after the dew condensation
conditions) for 800 hours. Then, a UV ray cutting rate thereof in
340 nm was measured by means of a spectrophotometer (U-4000 (model
number)), manufactured by Hitachi High-Technologies Corporation)
and evaluated according to the following criteria to set it to
evaluation of the UV ray blocking persistence: [0375]
.circleincircle.: UV ray cutting rate is 95% or more [0376]
.largecircle.: UV ray cutting rate is 90% or more and less than 95%
[0377] .DELTA.: UV ray cutting rate is 70% or more and less than 90
[0378] X: UV ray cutting rate is less than 70%
(3-4) Harmful Insect Activity Inhibiting Effect:
[0379] The films obtained in the examples and the comparative
examples were used, and movement of harmful insects in a plastic
house was visually observed and evaluated according to the
following criteria: [0380] .circleincircle.: harmful insects
scarcely moved [0381] .largecircle.: harmful insects moved slightly
[0382] X: harmful insects moved actively
(3-5) Evaluation of Weatherability (Evaluation of Appearance):
[0383] The films obtained in the examples and the comparative
examples were set in Metal Weather (manufactured by DAIPLA WINTES
Co., Ltd.) and subjected to a weatherability test in which they
were left standing on light conditions (illuminance: 60
mW/cm.sup.2, black panel temperature: 63.degree. C., humidity in
the layer: 50% RH) for 20 hours, on dew condensation conditions
(illuminance: 0 mW/cm.sup.2, black panel temperature: 30.degree.
C., humidity in the layer: 98% RH) for 4 hours and on a water
spraying condition (10 seconds before and after the dew
condensation conditions) for 800 hours. After the above test, the
films were held for 2 days on the conditions of 25.degree. C. and
50% RH, and then an appearance of cracks and whitening on a surface
of the sheet was evaluated according to the following criteria:
[0384] .circleincircle.: appearance change was not observed at all
[0385] .largecircle.: appearance change was scarcely observed
[0386] .DELTA.: appearance change was slightly observed, but
problems were not involved practically [0387] X: appearance change
was notably observed (3-6) Evaluation of Tensile Strength after
Stretched Over a Long Period (Evaluation of Weatherability Holding
Property):
[0388] The films obtained in the examples and the comparative
examples were set in Eye Super UV Tester (manufactured by Iwasaki
Electric Co., Ltd.), and the films were subjected to a
weatherability test in which they were left standing on light
conditions (illuminance: 60 mW/cm.sup.2, black panel temperature:
63.degree. C., humidity in the layer: 50% RH) for 20 hours, on dew
condensation conditions (illuminance: 0 mW/cm.sup.2, black panel
temperature: 30.degree. C., humidity in the layer: 98% RH) for 4
hours and on a water spraying condition (10 seconds before and
after the dew condensation conditions) for 100 hours. Then, a
tensile strength of the films was measured according to JIS K6732
by means of a tensilon universal test instrument (RTC-1250A type,
manufactured by Orientec Electric Co., Ltd.) to evaluate a
proportion of the tensile strength as compared with that before the
above weatherability test according to the following criteria:
[0389] .circleincircle.: 80% or more [0390] .largecircle.: 60% or
more and less than 80% [0391] .DELTA.: 30% or more and less than
60% [0392] X: less than 30%
(3-7) Evaluation of Heat Fusion Property:
[0393] The films obtained in the examples and the comparative
examples were pressed (thermally fused) for 1 minute on the
conditions of 160.degree. C. and 2.0 kgf/cm.sup.2 with the faces of
the coating layers B being opposite, and then the T type peeling
strengths thereof were measured according to JIS K6854-3 by means
of the tensilon universal test instrument (RTC-1250A type,
manufactured by Orientec Electric Co., Ltd.) to evaluate them
according to the following criteria: [0394] .circleincircle.: 20N
or more [0395] .largecircle.: 10N or more and less than 20N [0396]
.DELTA.: 3N or more and less than 10N [0397] X: less than 3N
(3-8) Evaluation of Drip-Proof Property (Initial Performance) and
Persistence Thereof:
[0398] The films obtained in the examples and the comparative
examples were used to measure contact angles thereof with water by
means of a contact angle meter (CA-X type (model number),
manufactured by Kyowa Interface Science Co., Ltd.), and they were
evaluated according to the following criteria. Further, the films
obtained in the examples and the comparative examples were dipped
in warm water of 40.degree. C. for 1 month and then naturally dried
at 25.degree. C. for 24 hours, and the films were evaluated in the
same manner as described above to set it to evaluation of a
persistence of the drip-proof property.
[0399] .circleincircle.: contact angle is less than 50.degree.
[0400] .largecircle.: contact angle is 50.degree. or more and less
than 60.degree. [0401] .DELTA.: contact angle is 60.degree. or more
and less than 75.degree. [0402] X: contact angle is 75.degree. or
more
Example 3-1
[0403] A resin film comprising a transparent polypropylene resin
(thickness: 100 .mu.m) was prepared as the base material. A surface
and a rear face thereof were subjected to corona discharge
treatment, and then a composition for forming a primer layer having
the following composition was coated (2.5 g/m.sup.2) on one face
thereof to form a primer layer (thickness: 2 .mu.m). Next, an
ionizing radiation-curable resin composition containing a silicate
compound having a reactive functional group, a UV absorber and a
light stabilizer which had the following composition was prepared
to form a coating film by a gravure coating method, and the coating
film described above was cross-linked and cured by irradiating with
an electron beam on the conditions of 175 keV and 5 Mrad (50 kGy),
whereby a surface protective layer (10 g/m.sup.2) was formed.
[0404] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
Composition of Resin Composition for Forming a Primer Layer:
[0405] It is a composition obtained by mixing a resin composition
and a curing agent each shown below in a proportion of 100:5 (mass
ratio).
Resin Composition:
TABLE-US-00008 [0406] Polycarbonate base urethane/acryl copolymer
resin 100 parts by mass Hydroxyphenyltriazine base UV absorber 20
parts by mass (Tinuvin 400 (trade name), manufactured by BASF Japan
Ltd.) Hindered amine base light stabilizer (Tinuvin 123 15 parts by
mass (trade name), manufactured by BASF Japan Ltd.) Silica (average
particle diameter: 5 .mu.) 10 parts by mass
Curing Agent:
[0407] Hexamethylenediisocyanate
Composition of Ionizing Radiation-Curable Resin Composition:
TABLE-US-00009 [0408] Caprolactone base urethane acrylate oligomer
100 parts by mass (trifunctional, weight average molecular weight:
1200) Silicate compound represented by Chemical Formula (4) 5 parts
by mass described above which has a vinyl group at an end Triazine
base UV absorber (Tinuvin 479 (trade name), 6 parts by mass
2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,
6-bis(4-phenylphenyl)-1,3,5-triazine, manufactured by BASF Japan
Ltd.) Light stabilizer having a reactive functional group 6 parts
by mass (trade name: Sanol LS-3410, 1,2,2,
6,6-pentamethyl-4-piperidinyl methacrylate, manufactured by BASF
Japan Ltd.)
Example 3-2
[0409] A resin film comprising a transparent polypropylene resin
(thickness: 100 .mu.m) was prepared as the base material. A surface
and a rear face thereof were subjected to corona discharge
treatment, and then the composition for forming a primer layer used
in Example 3-1 was coated (2.5 g/m.sup.2) on one face thereof to
form a primer layer (thickness: 2 .mu.m). Next, the ionizing
radiation-curable resin composition containing a silicate compound
having a reactive functional group, a UV absorber and a light
stabilizer used in Example 3-1 was prepared to form a coating film
by a gravure coating method, and the coating film described above
was cross-linked and cured by irradiating with an electron beam on
the conditions of 175 keV and 5 Mrad (50 kGy), whereby a surface
protective layer (10 g/m.sup.2) was formed. Further, a coating
composition containing silica particles which had the following
composition was prepared, and the above coating composition was
coated on a face opposite to the surface protective layer described
above to form a coating film by a gravure coating method. The
coating film described above was cross-linked and cured by
irradiating with an electron beam on the conditions of 175 keV and
5 Mrad (50 kGy), whereby a rear surface coating layer (1 g/m.sup.2)
was formed to obtain a sheet having coating layers on both
surfaces.
[0410] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
Composition of Coating Agent:
TABLE-US-00010 [0411] Urethane acrylate base oligomer
(trifunctional, 10 parts by mass weight average molecular weight:
1200) Silica sol (IPA-ST (trade name), average 100 parts by mass
primary particle diameter: 5 to 15 nm, IPA dispersion, solid matter
content: 15%, manufactured by Nissan Chemical Industries, Ltd.
Example 3-3
[0412] A sheet was obtained in the same manner as in Example 3-1,
except that in Example 3-1, the hydrophilizing agent was changed
from the silicate compound having a vinyl group at an end to
non-reactive alkyl silicate 3-1 (MS-56S (trade name), manufactured
by Mitsubishi Chemical Corporation, an average hexadecamer (mixture
of a tetradecamer to an octadodecamer) of alkyl silicate in which
all of R.sup.12 to R.sup.15 in Formula (3) described above are
methyl, weight average molecular weight: 1500 to 1900).
[0413] The film thus obtained was evaluated for the items described
above, and the evaluation results thereof are shown in Table 4.
Example 3-4
[0414] A sheet was obtained in the same manner as in Example 3-1,
except that in Example 3-1, 10 parts by mass of a benzotriazole
base UV absorber (Tinuvin 109 (trade name), manufactured by BASF
Japan Ltd.) was added further to the ionizing radiation-curable
resin composition.
[0415] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
Example 3-5
[0416] A sheet was obtained in the same manner as in Example 3-1,
except that in Example 3-1, the hydrophilizing agent was changed to
alkyl silicate 3-2 (MS-56 (trade name), manufactured by Mitsubishi
Chemical Corporation, an average decamer (mixture of a decamer to a
dodecamer) of alkyl silicate in which all of R.sup.12 to R.sup.15
in Formula (3) described above are methyl, weight average molecular
weight: 1100 to 1300, manufactured by Mitsubishi Chemical
Corporation).
[0417] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
Example 3-6
[0418] A sheet was obtained in the same manner as in Example 3-1,
except that in Example 3-1, the hydrophilizing agent was changed to
alkyl silicate 3-3 (Methyl Silicate 53A (trade name), an average
heptamer of alkyl silicate in which all of R.sup.12 to R.sup.15 in
Formula (3) described above are methyl, weight average molecular
weight: 789, manufactured by COLCOAT CO., Ltd.).
[0419] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
Example 3-7
[0420] A sheet was obtained in the same manner as in Example 3-1,
except that in Example 3-1, the hydrophilizing agent was changed to
alkyl silicate 3-4 having methoxy and ethoxy (EMS-485 (trade name),
an average decamer of alkyl silicate in which R.sup.12 and R.sup.13
in Formula (3) described above are methyl and in which R.sup.14 and
R.sup.15 are ethyl, weight average molecular weight: 1300,
manufactured by COLCOAT CO., Ltd.).
[0421] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
Comparative Example 3-1
[0422] A sheet was obtained in the same manner as in Example 3-1,
except that in Example 3-1, the surface protective layer was not
provided.
[0423] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
Comparative Example 3-2
[0424] A sheet was obtained in the same manner as in Example 3-1,
except that in Example 3-1, the ionizing radiation-curable resin
composition was changed from the caprolactone base urethane
acrylate to a urethane acrylate base oligomer (hexafunctional,
weight average molecular weight: 2000).
[0425] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
Comparative Example 3-3
[0426] A sheet was obtained in the same manner as in Example 3-1,
except that in Example 3-1, a resin composition obtained by
removing the silicate compound having a vinyl group at an end from
the ionizing radiation-curable resin composition was used.
[0427] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 4.
TABLE-US-00011 TABLE 4 Comparative Example Example 3-1 3-2 3-3 3-4
3-5 3-6 3-7 3-1 3-2 3-3 Ionizing radiation-curable resin
composition Caprolactone base urethane acrylate 100 100 100 100 100
100 100 -- -- 100 Hexafunctional urethane acrylate -- -- -- -- --
-- -- -- 100 -- Silicate Having reactive 5 5 -- 5 -- -- -- -- 5 --
compound functional group Alkyl silicate 3-1 -- -- 5 -- -- -- -- --
-- -- Alkyl silicate 3-2 -- -- -- -- 5 -- -- -- -- -- Alkyl
silicate 3-3 -- -- -- -- -- 5 -- -- -- -- Alkyl silicate 3-4 -- --
-- -- -- -- 5 -- -- -- UV Triazine base 6 6 6 6 6 6 6 -- 6 6
absorber Benzotiazole base -- -- -- 10 -- -- -- -- -- -- Light
Reactive hindered amine 6 6 6 6 6 6 6 -- 6 6 stabilizer base
Coating agent Trifunctional urethane acrylate -- 10 -- -- -- -- --
-- -- -- Silica sol (solid matter content: -- 100 -- -- -- -- -- --
-- -- 15%): drip-proof agent Evaluation Self-cleaning .largecircle.
.largecircle. .circleincircle. .largecircle. .circleincircle.
.largecircle. .largecircle. .DELTA. .largecircle. .largecircle.
performance (initial) Persistence of self- .circleincircle.
.circleincircle. .largecircle. .circleincircle. .largecircle.
.largecircle. .largecircle. X .circleincircle. .circleincircle.
cleaning performance Visible light .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
transmission property (initial) Persistence of visible
.circleincircle. .circleincircle. .largecircle. .circleincircle.
.largecircle. .largecircle. .largecircle. X .circleincircle.
.circleincircle. light transmission property UV ray blocking
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. X .largecircle.
.largecircle. persistence Harmful insect activity .largecircle.
.largecircle. .largecircle. .circleincircle. .largecircle.
.largecircle. .largecircle. X .largecircle. .largecircle.
inhibiting effect Weatherability .largecircle. .largecircle.
.largecircle. .circleincircle. .largecircle. .largecircle.
.largecircle. X .DELTA. .largecircle. (appearance) Tensile strength
after .largecircle. .largecircle. .largecircle. .circleincircle.
.largecircle. .largecircle. .largecircle. X .DELTA. .largecircle.
stretched over a long period Thermal fusion property .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. X .largecircle. .largecircle.
Drip-proof property -- .largecircle. -- -- -- -- -- -- --
.largecircle. (initial) Persistence of drip- -- .largecircle. -- --
-- -- -- -- -- .DELTA. proof property Remark: all the values of the
coating agents show parts by mass.
4. Coating Composition 4 and Sheet 4
Examples 4-1 to 4-3 and Comparative Examples 4-1 to 4-5
Preparation of Sheets:
[0428] A resin sheet comprising a transparent polypropylene resin
(thickness: 80 .mu.m) was prepared as the base material.
[0429] A surface and a rear face thereof were subjected to corona
discharge treatment, and then a primer agent was coated on the
above surface to form a primer layer (thickness: 2 .mu.m, 2.5
g/m.sup.2). The primer agent was a mixture of 100 parts by mass of
a resin composition and 5 parts by mass of
hexamethylenediisocyanate (curing agent), and the resin composition
described above was a mixture of a polycarbonate base urethane
acryl copolymer, acrylpolyol, a triazine base UV absorber (15% by
mass) and a hindered amine base light stabilizer (3% by mass).
[0430] Next, 8 kinds of coating compositions were prepared by
mixing a base resin, an oil repellent agent and a hydrophilizing
agent as shown in the following Table 4-1. Then, each coating
composition was coated on the primer layer by a gravure coating
method. Thereafter, the coating film was cross-linked and cured by
irradiating with an electron beam on the conditions of 175 keV and
5 Mrad (50 kGy), whereby a surface protective layer (5 g/m.sup.2)
having a thickness of 5 .mu.m was formed to obtain a sheet.
Evaluation of Sheets:
[0431] A self-cleaning property, a self-cleaning effect developing
rate, an abrasion resistance, a warm water resistance, a
weatherability and a scratch resistance of the respective sheets
were checked. The respective test methods and evaluation criteria
are shown below.
Self-Cleaning Property:
[0432] Test method: an outdoor exposure test (the sheets were left
standing outdoors (toward the south at a gradient of 45.degree.)
for 2 to 3 months) was carried out. Then, the appearances of the
respective sheets were observed to evaluate an adhesion and
deposition degree of contaminants: [0433] .largecircle.: adhesion
and deposition of contaminants were not observed [0434] .DELTA.:
adhesion of contaminants was observed, but deposition thereof was
not observed [0435] X: adhesion and deposition of contaminants were
observed
Self-Cleaning Effect Developing Rate:
[0436] Test method: the sheets were left standing indoors, and then
time passing until a hydrophilicity of the respective sheets was
developed was evaluated: [0437] .largecircle.: within 1 week [0438]
.DELTA.: 1 week or longer and shorter than 2 months [0439] X: 2
months or longer
Abrasion Resistance:
[0440] Test method: the sheets were subjected to a rubbing test
with a gauze (load: 1500 g, 50 reciprocations), and then a
hydrophilic performance thereof was evaluated: [0441]
.largecircle.: no change [0442] .DELTA.: slightly reduced [0443] X:
the performance was lost
Warm Water Resistance:
[0444] Test method: the sheets were dipped in warm water of
80.degree. C. for 3 days, and the appearances of the respective
sheets were evaluated: [0445] .largecircle.: no appearance change
[0446] .DELTA.: slightly whitened [0447] X: notably whitened
Weatherability:
[0448] Test method: the sheet was put in S-W.O.M. (manufactured by
Suga Test Instruments Co., Ltd.: test conditions are based on JIS
A1415), and the appearances of the respective sheets were observed
after 4000 hours passed: [0449] .largecircle.: no appearance change
[0450] .DELTA.: slightly changed [0451] X: notably changed
Scratch Resistance:
[0452] Test method: after a nail marling test (rubbing the sheet in
20 reciprocations by nail), the appearances of the respective
sheets were evaluated: [0453] .largecircle.: no appearance change
[0454] .DELTA.: no scratches were observed, but gloss change was
observed [0455] X: scratches were observed
TABLE-US-00012 [0455] TABLE 5 Example Comparative Example 4-1 4-2
4-3 4-1 4-2 4-3 4-4 4-5 4-6 Base Base 1 100 100 -- 100 100 100 100
-- -- component Base 2 -- -- 100 -- -- -- -- -- -- Base 3 -- -- --
-- -- -- -- 100 -- Base 4 -- -- -- -- -- -- -- -- 100 Oil Fluorine
-- -- -- -- 20 -- 20 -- -- repellent base agent resin
Hydrophilizing Methyl 10 5 10 -- -- -- -- 10 10 agent silicate
Ethyl -- 5 -- -- -- 10 -- -- -- silicate UV Triazine Contained
Contained Contained Contained Contained Contained Contained Not Not
absorber base contained contained Light Hindered Contained
Contained Contained Contained Contained Contained Contained Not Not
stabilizer amine contained contained base Evaluation Self-
.largecircle. .largecircle. .largecircle. X X .DELTA. X
.largecircle. .DELTA. cleaning property Self- .largecircle.
.largecircle. .largecircle. X X X X .largecircle. .largecircle.
cleaning effect developing rate Abrasion .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. X .largecircle. to .DELTA. resistance
Warm water .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. X .DELTA. resistance
Weatherability .largecircle. .largecircle. .DELTA. .largecircle.
.largecircle. .largecircle. .largecircle. X .largecircle. to
.DELTA. Scratch .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. X
.largecircle. to .DELTA. resistance
[0456] In Table 5, the base 1 was caprolactone base urethane
acrylate, and trifunctional urethane acrylate having a weight
average molecular weight of 1200 was used as the above caprolactone
base urethane acrylate. The base 2 was non-caprolactone base
urethane acrylate, and 3.9 functional urethane acrylate having a
weight average molecular weight of 2000 was used therefor.
[0457] The base 3 is a polyester base one-component liquid coating
agent (conventional product), and ASCA BAKE NEO (trade name)
manufactured by Kansai Paint Co., Ltd. was used therefor. Also, the
base 4 is an acryl urethane base two-component liquid coating agent
(conventional product), and SUPER RETAN 1000 (trade name)
manufactured by Kansai Paint Co., Ltd. was used therefor.
[0458] Methyl Silicate 53A (trade name) manufactured by COLCOAT
CO., Ltd. (an average heptamer of alkyl silicate in which all of
R.sup.12 to R.sup.15 in Formula (3) described above are methyl, a
weight average molecular weight: 789) was used as the methyl
silicate in Examples 1 and 3 and Comparative Examples 4 and 5.
EMS-485 (trade name) manufactured by COLCOAT CO., Ltd. (an average
decamer of alkyl silicate in which R.sup.12 and R.sup.13 in Formula
(3) described above are methyl and in which R.sup.14 and R.sup.15
are ethyl, weight average molecular weight: 1300) was used as the
hydrophilizing agent in Example 2. Also, Ethyl Silicate 48 (trade
name) manufactured by COLCOAT CO., Ltd. (decamer, molecular weight:
1400) was used as the ethyl silicate in Comparative Example 3.
[0459] Further, Lumiflon (trade name) manufactured by Asahi Glass
CO., Ltd. was used as the fluorine base resin (oil repellent
agent).
5. Coating Composition 5 and Sheet 5
Evaluation Methods:
(5-1) Evaluation of Self-Cleaning Performance (Initial Performance)
and Persistence Thereof:
[0460] The sheets obtained in the examples and the comparative
examples were set outdoors toward the south at a gradient of
45.degree.. Then, an adhesion and deposition state of contaminants
on the surface was evaluated by visual observation according to the
following criteria to set it to evaluation of the initial
performance. Further, the sheets obtained in the examples and the
comparative examples were subjected to an outdoor exposure test in
which they were set outdoors toward the south at a gradient of
45.degree. and then left standing for 3 months. Then, an adhesion
and deposition state of contaminants on the surface was evaluated
by visual observation according to the following criteria to set it
to evaluation of the persistence: [0461] .circleincircle.: adhesion
and deposition of contaminants were not confirmed at all [0462]
.largecircle.: adhesion and deposition of contaminants were
scarcely observed [0463] .DELTA.: adhesion and deposition of
contaminants were slightly observed, but problems were not involved
practically [0464] X: adhesion and deposition of contaminants were
notably observed
(5-2) Evaluation of Warm Water Whitening Resistance:
[0465] The sheets obtained in the examples and the comparative
examples were dipped in warm water of 80.degree. C. for 7 days. An
appearance of the sheet after dipped was evaluated by visual
observation according to the following criteria: [0466]
.circleincircle.: appearance change was not observed at all [0467]
.largecircle.: appearance change was scarcely observed [0468]
.DELTA.: appearance was slightly whitened, but problems were not
involved practically [0469] X: appearance was notably whitened
(5-3) Evaluation of Weatherability (Evaluation of Appearance):
[0470] The sheets obtained in the examples and the comparative
examples were set in Metal Weather manufactured by DAIPLA WINTES
Co., Ltd. and subjected to a weatherability test in which they were
left standing on light conditions (illuminance: 60 mW/cm.sup.2,
black panel temperature: 63.degree. C., humidity in the layer: 50%
RH) for 200 hours, on dew condensation conditions (illuminance: 0
mW/cm.sup.2, black panel temperature: 30.degree. C., humidity in
the layer: 98% RH) for 4 hours and on a water spraying condition
(10 seconds before and after the dew condensation conditions) for
800 hours. After the above test, the sheets were held for 2 days on
the conditions of 25.degree. C. and 50% RH, and then an appearance
of cracks and whitening on a surface of the sheet was evaluated by
visual observation according to the following criteria: [0471]
.circleincircle.: appearance change was not observed at all [0472]
.largecircle.: appearance change was scarcely observed [0473]
.DELTA.: appearance change was slightly observed, but problems were
not involved practically [0474] X: appearance change was notably
observed
(5-4) Evaluation of Stickiness:
[0475] The sheets obtained in the examples and the comparative
examples were stored for 24 hours on the condition of 80.degree.
C., and then a surface of the above sheet was touched with a finger
to evaluate a stickiness thereof according to the following
criteria: [0476] .circleincircle.: stickiness was not observed at
all [0477] .largecircle.: stickiness was scarcely observed [0478]
.DELTA.: stickiness was slightly observed, but problems were not
involved practically [0479] X: stickiness was notably observed
(5-5) Evaluation of Solvent Resistance:
[0480] A gauze was set to a plummet of 300 g/cm.sup.2 by a rubber
band and impregnated with ethyl acetate. Then, the above plummet
was reciprocated 50 times in a lateral direction on the surfaces of
the sheets obtained in the examples and the comparative examples,
and the surfaces of the sheets were evaluated by visual observation
according to the following criteria: [0481] .largecircle.: change
on the surface of the sheet was not observed at all [0482] .DELTA.:
change on the surface of the sheet was slightly observed, but
problems were not involved practically [0483] X: change on the
surface of the sheet was notably observed
(5-6) Transparency:
[0484] The appearances of the sheets obtained in the examples and
the comparative examples were visually observed and evaluated
according to the following criteria: [0485] .largecircle.: haze
feeling (cloudy feeling) was not observed at all [0486] .DELTA.:
haze feeling (cloudy feeling) was slightly observed, but problems
were not involved practically [0487] X: haze feeling (cloudy
feeling) was notably observed
(5-7) Scratch Resistance:
[0488] The sheets obtained in the examples and the comparative
examples were rubbed thereon in five reciprocations by using a
steel wool on which a weight of 300 g/cm.sup.2 was applied, and
then the surfaces of the above sheets were evaluated by visual
observation according to the following criteria: [0489]
.largecircle.: change was scarcely observed on the surface [0490]
.DELTA.: slight scratches and gloss change were observed on the
surface, but problems were not involved practically [0491] X:
marked scratches were observed on the surface, and gloss change was
notably observed as well
Example 5-1
[0492] A resin film comprising a transparent polypropylene resin
(thickness: 80 .mu.m) was prepared as the base material. A surface
thereof was subjected to corona discharge treatment, and then a
composition for forming a primer layer having the following
composition was coated (2.5 g/m.sup.2) on the above surface to form
a primer layer (thickness: 2 .mu.m). Next, a coating agent having
the following composition was prepared to form a coating film by a
gravure coating method, and the coating film described above was
cross-linked and cured by irradiating with an electron beam on the
conditions of 175 keV and 5 Mrad (50 kGy), whereby a surface
protective layer (5 g/m.sup.2) was formed. A thickness of the
surface protective layer thus obtained was 5 .mu.m.
[0493] The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 6.
Composition of Composition for Forming a Primer Layer:
[0494] It is a composition obtained by mixing a resin composition
and a curing agent each shown below in a proportion of 100:5.
Resin Composition:
TABLE-US-00013 [0495] Polycarbonate base urethane/acryl copolymer
resin 100 parts by mass Hydroxyphenyltriazine base UV absorber
(Tinuvin 400 15 parts by mass (trade name), manufactured by BASF
Japan Ltd.) Hindered amine base light stabilizer (Tinuvin 123 3
parts by mass (trade name), manufactured by BASF Japan Ltd.)
Curing Agent:
[0496] Hexamethylenediisocyanate
Composition of Coating Agent:
TABLE-US-00014 [0497] Caprolactone base urethane acrylate oligomer
100 parts by mass (trifunctional, weight average molecular weight:
1200) Alkyl silicate 5-1 (an average 26-mer (mixture 10 parts by
mass of a 24-mer to a 28-mer) of alkyl silicate in which all of
R.sup.1 to R.sup.4 in Formula (1) described above are methyl,
weight average molecular weight: 2500 to 2900) Triazine base UV
absorber (Tinuvin 479 (trade name), 1 part by mass
2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,
6-bis(4-phenylphenyl)-1,3,5-triazine, manufactured by BASF
JapanLtd.) Light stabilizer having a reactive functional group 2
parts by mass (trade name: Sanol LS-3410, 1,2,2,6, 6-pentamethyl-
4-piperidinyl methacrylate, manufactured by BASF Japan Ltd.)
Example 5-2
[0498] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the caprolactone base urethane acrylate
oligomer contained in the coating agent was changed to a polyether
base acrylate oligomer (difunctional, molecular weight: 3000). The
sheet thus obtained was evaluated for the items described above,
and the evaluation results thereof are shown in Table 6.
Example 5-3
[0499] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the alkyl silicate 5-1 contained in the
coating agent was changed to other alkyl silicate 5-2 (an average
31-mer (a mixture of a 29-mer to a 33-mer) of alkyl silicate in
which all of R.sup.1 to R.sup.4 in Formula (1) described above are
methyl, weight average molecular weight: 3000 to 3400). The sheet
thus obtained was evaluated for the items described above, and the
evaluation results thereof are shown in Table 6.
Example 5-4
[0500] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the alkyl silicate 5-2 contained in the
coating agent was changed to other alkyl silicate 5-3 (an average
24-mer (a mixture of a 22-mer to a 26-mer) of alkyl silicate in
which R.sup.1 and R.sup.3 in Formula (1) described above are methyl
and in which R.sup.2 and R.sup.4 are ethyl, weight average
molecular weight: 2700 to 3200). The sheet thus obtained was
evaluated for the items described above, and the evaluation results
thereof are shown in Table 6.
Example 5-5
[0501] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the alkyl silicate 5-1 contained in the
coating agent was changed to other alkyl silicate 5-4 (an average
23-mer (a mixture of a 21-mer to a 25-mer) of alkyl silicate in
which R.sup.1 to R.sup.4 in Formula (1) described above are ethyl,
weight average molecular weight: 2900 to 3400). The sheet thus
obtained was evaluated for the items described above, and the
evaluation results thereof are shown in Table 6.
Comparative Example 5-1
[0502] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the alkyl silicate 5-1 contained in the
coating agent was changed to alkyl silicate 5-5 (MS-56 (trade
name), manufactured by Mitsubishi Chemical Corporation, an average
decamer (mixture of a decamer to a dodecamer) of alkyl silicate in
which all of R.sup.1 to R.sup.4 in Formula (1) described above are
methyl, weight average molecular weight: 1100 to 1300). The sheet
thus obtained was evaluated for the items described above, and the
evaluation results thereof are shown in Table 6.
Comparative Example 5-2
[0503] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the alkyl silicate 5-1 contained in the
coating agent was changed to alkyl silicate 5-6 (MS-56S (trade
name), manufactured by Mitsubishi Chemical Corporation, an average
hexadecamer (mixture of a tetradecamer to an octadodecamer) of
alkyl silicate in which all of R.sup.1 to R.sup.4 in Formula (1)
described above are methyl, weight average molecular weight: 1500
to 1900). The sheet thus obtained was evaluated for the items
described above, and the evaluation results thereof are shown in
Table 6.
Comparative Example 5-3
[0504] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the alkyl silicate 5-1 contained in the
coating agent was changed to the alkyl silicate 5-6 described above
and that the caprolactone base urethane acrylate oligomer was
changed to a polyether base acrylate oligomer (difunctional,
molecular weight: 3000). The sheet thus obtained was evaluated for
the items described above, and the evaluation results thereof are
shown in Table 6.
Comparative Example 5-4
[0505] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the alkyl silicate 5-1 contained in the
coating agent was changed to alkyl silicate 5-7 (Methyl Silicate 51
(trade name), manufactured by COLCOAT CO., Ltd., an average
heptamer of alkyl silicate in which all of R' to R.sup.4 in Formula
(1) described above are methyl, weight average molecular weight:
789). The sheet thus obtained was evaluated for the items described
above, and the evaluation results thereof are shown in Table 6.
Comparative Example 5-5
[0506] A sheet was obtained in the same manner as in Example 5-1,
except that in Example 5-1, the alkyl silicate 5-1 contained in the
coating agent was changed to alkyl silicate 5-8 having methoxy and
ethoxy (EMS-485 (trade name), manufactured by COLCOAT CO., Ltd., an
average decamer of alkyl silicate in which R.sup.1 and R.sup.3 in
Formula (1) described above are methyl and in which R.sup.2 and
R.sup.4 are ethyl, weight average molecular weight: 1300). The
sheet thus obtained was evaluated for the items described above,
and the evaluation results thereof are shown in Table 6.
Comparative Example 5-6
[0507] A sheet was obtained in the same manner as in Example 5-1,
except that in Comparative Example 5-4, the caprolactone base
urethane acrylate oligomer contained in the coating agent was
changed to a polyether base acrylate oligomer (difunctional, weight
average molecular weight: 3000). The sheet thus obtained was
evaluated for the items described above, and the evaluation results
thereof are shown in Table 6.
TABLE-US-00015 TABLE 6 Example Comparative Example Coating agent
5-1 5-2 5-3 5-4 5-5 5-1 5-2 5-3 5-4 5-5 5-6 Caprolactone base
urethane 100 -- 100 100 100 100 100 -- 100 100 -- acrylate
Polyether base urethane acrylate -- 100 -- -- -- -- -- 100 -- --
100 Alkyl Alkyl silicate 5-1 10 10 -- -- -- -- -- -- -- -- --
silicate Alkyl silicate 5-2 -- -- 10 -- -- -- -- -- -- -- -- Alkyl
silicate 5-3 -- -- -- 10 -- -- -- -- -- -- -- Alkyl silicate 5-4 --
-- -- -- 10 -- -- -- -- -- -- Alkyl silicate 5-5 -- -- -- -- -- 10
-- -- -- -- -- Alkyl silicate 5-6 -- -- -- -- -- -- 10 10 -- -- --
Alkyl silicate 5-7 -- -- -- -- -- -- -- -- 10 -- 10 Alkyl silicate
5-8 -- -- -- -- -- -- -- -- -- 10 -- Evaluation Self-cleaning
.circleincircle. .circleincircle. .circleincircle. .largecircle.
.circleincircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. performance (initial)
Persistence of .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .DELTA. .DELTA. .DELTA. .DELTA.
.DELTA. .DELTA. self-cleaning performance Warm water whitening
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. .DELTA.
.DELTA. .DELTA. resistance Weatherability .largecircle. .DELTA.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .DELTA. .largecircle. .largecircle. .DELTA.
Stickiness .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. .DELTA.
.DELTA. .DELTA. Solvent resistance .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .DELTA. .DELTA. .DELTA. Transparency
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle. .DELTA.
.DELTA. .DELTA. Scratch resistance .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. Remark: all the values of the coating agents show
parts by mass.
[0508] It has been confirmed that the sheets obtained in Examples
5-1 to 5-3 show excellent effects in all evaluations and that they
show very excellent effects in terms of particularly a
self-cleaning performance (initial) and a persistence thereof. On
the other hand, it has been confirmed that the sheets obtained in
Comparative Examples 5-1 to 5-6 are not satisfactory in terms of a
persistence of a self-cleaning performance, a warm water whitening
resistance, a stickiness, a solvent resistance and a transparency
and that when the higher performances are required, there is a room
of improvement.
INDUSTRIAL APPLICABILITY
[0509] The coating compositions of the present invention can
provide sheets with a visible light transmission property and a UV
ray-blocking performance in addition to an excellent self-cleaning
performance and a persistence thereof, a weatherability and a
persistence thereof and a transparency. Accordingly, the coating
compositions and the coating films of the present invention are
suitably used for applications in entrance doors and exterior
materials in general housings, interiors and exteriors such as
floor materials, outside walls and the like in public facilities,
buildings and structures installed outdoors.
* * * * *